20070812 Ver 1_08 Fish Sampling Work Plan (2)_20080502

FISH SAMPLING WORK PLAN
NARROWS RESERVOIR
BADIN, NORTH CAROLINA
Prepared for
Alcoa, Inc.
2300 N. Wright Road
Alcoa, Tennessee 37701
December 14, 2007
Project Number: 20500252.00001
FISH SAMPLING WORK PLAN
NARROWS RESERVOIR
BADIN, NORTH CAROLINA
Prepared for:
Alcoa, Inc.
2300 N. Wright Road
Alcoa, Tennessee 37701
December 2007
URS Corporation
1000 Corporate Centre Drive
Suite 250
Franklin, TN 37067
Project #20500252.00001
TABLE OF CONTENTS
1 Introduction .........................................................................................................................1-1
1.1 Site History ................................................................................................................. 1-1
2 Fish Tissue Monitoring .......................................................................................................2-1
2.1 Fish Tissue Monitoring ................................................................ ............................... 2-1
2. 1.1 General Approach ............................................................... ...............................2-1
2.2 Sampling Site Selection ............................................................... ............................... 2-1
2.3 Field and Laboratory Methods ..................................................... ...............................2-2
2.3.1 Sampling Method ............................................................... ............................... 2-2
2.3.2 Sample Identification .......................................................... ...............................2-3
2.3.3 Analytical Methodology ..................................................... ...............................2-3
2.3.4 QA/QC ................................................................................ ...............................2-4
2.3.4.1 Decontamination Procedures ............................... ............................... 2-4
2.3.4.2 Sample Custody ................................................... ............................... 2-5
2.3.4.3 Sample Shipping .................................................. ............................... 2-5
2.3.5 Derived Waste Management .............................................. ............................... 2-5
3 Reporting Schedule .............................................................................................................3-1
3.1 Reporting and Schedule .............................................................................................. 3-1
4 References ............................................................................................................................4-1
LIST OF FIGURES
Figure 1-1 Site Location
Figure 2-1 Fish Sampling Locations
APPENDICES
Appendix A BHE Environmental Analytical Data
Appendix B Quality Assurance/Quality Control
i
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SECTIONONE Introduction
1.1 SITE HISTORY
Alcoa Power Generating Inc. (APGI), a wholly-owned subsidiary of Alcoa Inc. (Alcoa) operates
four hydroelectric developments, the High Rock, Tuckertown, Narrows and Falls developments,
which are located on a 38-mile stretch of the Yadkin River. Narrows was the first of the Project
developments to be built (Figure 1-1).
In the early 1900s, the Southern Aluminum Company, a subsidiary of L'Aluminum Francaise,
constructed two bypass tunnels on the east side of the Yadkin River to divert water around a
planned Narrows Dam and Powerhouse construction site. A large amount of rock spoil from the
tunnels construction was piled along the southeastern side of the Powerhouse. Southern
Aluminum Company was sold to Alcoa in November 1915, who completed the Narrows Dam
and Powerhouse by June 1917.
The rock spoil from the tunnels construction currently sits on a bedrock ridge, which creates a
semi-isolated cove directly in the mouth of the bypass tunnels. This cove is located
approximately 35 feet below the Powerhouse, and is bordered by a shear rock face cliff on the
north, a nearly vertical bluff on the east, and by the bedrock ridge that forms the peninsula on the
western edge. The water surface area of the cove is approximately 0.15 acres. The peninsula is
comprised of exposed metavolcanic bedrock ridge and tunnel construction spoil consisting of
large boulders and cobbles. Very little sediment or soil is found on the peninsula. In the areas
where sediments/soils are present heavy vegetation has grown.
During the nearly 90 years of operation of the Powerhouse, various materials have fallen from
the Powerhouse onto the peninsula below. Materials such as sandblasting grit, electrical
equipment, broken glass, metal, brick and other miscellaneous rubble are found in a debris pile at
the base of the Powerhouse adjacent to the cove.
In 2001, two small electrical capacitors were discovered in the debris pile. These electrical
capacitors were removed by APG for offsite disposal. The electrical equipment, metal and brick
debris likely came from prior construction work on the Powerhouse. APG's best estimate is that
the capacitors were used as auxiliary electrical equipment during the period between the 1940s
and 1970s. The structure where the capacitors were located was removed sometime between
1973 and 1975. Alcoa believes that the capacitors were discarded during this time period. APG
bases this estimate upon reviews of engineering drawings and employee interviews.
Investigative activities were conducted at the Site in three phases (November 2001, February
2003, and August 2005). Shield Engineering, Inc. ("Shield") of Charlotte, North Carolina
managed all activities conducted in November 2001, and documented activities in an internal
Alcoa report dated January 9, 2002. Engineering Inc. managed investigation activities conducted
in February 2003 and August 2005. The complete results of these three phases are documented
in the report, "Investigation Summary Report", Alcoa Power Generating, Inc. - Yadkin Division
Narrows Dam Powerhouse (Engineering, Inc. 2006). A brief summary of each phase is
presented below.
1-1
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SECTIONONE Introduction
Soil samples collected at the Site in November 2001 indicated that concentrations of total PCBs
in excess of 50 milligrams per kilogram ("mg/kg") were detected in two of the fourteen soil
samples.
On February 24, 2003, Engineering Inc. personnel mobilized to the site to collect additional
sediment, soil, and surface water samples. A total of five sediment samples, one soil sample and
a single composite water sample were collected during this investigation. PCB concentrations
were less than 50 mg/kg in sediment and soil samples and the surface water was non-detect for
PCBs.
On August 25, 2005, Engineering Inc. personnel collected sediment and soil samples to further
define the horizontal and vertical distribution of impacted materials. A total of three sediment
samples were collected from the floor of the cove and nine soil samples were collected from the
debris pile and peninsula. Total PCBs concentrations in excess of 50 mg/kg were not detected in
any of the sediment or soil samples.
In summary, sediments impacted by PCBs and are generally localized to the submerged sediment
fan of the debris pile immediately east of the Powerhouse covering a surface area of approximately
870 square feet. Laboratory results from sediment samples indicated no concentrations of total
PCBs in excess of 50 mg/kg. Soils impacted by PCBs are generally localized to the debris pile
immediately east of the Powerhouse covering a surface area of approximately 3,200 square feet.
Laboratory results from soil samples indicated total PCBs in excess of 50 mg/kg in three of the
twenty-four soil samples collected. Concentrations of total PCBs in soil samples greater than 50
mg/kg ranged from 59 mg/kg to 140 mg/kg.
In September 2007, BBE Environmental (BBE) was contracted by Alcoa to collect additional
sediment samples from the cove which is adjacent to the area where PCBs were detected in soils.
BBE Environmental collected two sediment samples which were subsequently analyzed for
select PCB congeners, dioxin and furans. The data indicated that sediments contained detectable
levels of PCBs and dioxins. Analytical results are included in Appendix A. In cooperation with
the State of North Carolina, Alcoa contracted URS Corporation to prepare a Work Plan detailing
the procedures for obtaining fish samples to evaluate if PCBs and dioxins detected in sediments
are also detectable in biological tissue immediately below the Narrows Dam. Based on the
findings of the sediment analyses, a limited number of PCB and dioxin congeners were detected.
1-2
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SECTIONONE
Introduction
These included:
PCBs Dioxins
77-TeCB 2,3,7,8-TCDD
123-PeCB 1,2,3,4,6,7,8-HpCDD
118-PeCB OCDD
114-PeCB 2,3,7,8-TCDF
105-PeCB 1,2,3,7,8-PeCDF
126-PeCB 2,3,4,7,8-PeCDF
167-HxCB 1,2,3,4,7, 8-HxCDF
156,157-HxCB 1,2,3, 6,7, 8-HxCDF
169-HxCB 2,3,4, 6,7, 8-HxCDF
180,193-HpCB 1,2,3,7,8,9-HxCDF
170-HpCB 1,2,3,4,6,7,8-HpCDF
189-HpCB 1,2,3,4,7, 8,9-HpCDF
OCDF
The objective of this investigation is to evaluate whether these congeners have accumulated in
fish tissue. This Work Plan details the activities related to fish tissue collection and analytical
requirements.

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Drawn By:
Title: Site LOCationTDH
Figure 1-1
Revision Date:
10/17/07
Source:

SECTIONTWO Fish Tissue Monitoring
2.1 FISH TISSUE MONITORING
The objectives of the proposed fish tissue sampling event are to:
1) Determine if PCB and dioxins congeners detected in sediments in the Narrows Cove
have been released and subsequently have accumulated in fish collected adjacent to the
Narrows Cove;
2) Determine if PCB Aroclors are detected in fish tissue samples; and
3) Determine if the concentrations of PCB and dioxins congeners and PCB Aroclors
detected in fish tissue samples collected adjacent to the Narrows Cove are comparable to
background levels detected in tissues collected from an upgradient area not influenced by
the site.
2.1.1 General Approach
The fish tissue sampling will include collecting a bottom feeding species from an area adjacent
to the Narrows Cove as well as from a reference location in a northeastern arm of Badin Lake.
The target species will be channel catfish (Ictalurus punctatus). These fish represent bottom-
dwelling species which are commonly included in state and federal monitoring programs as
"worst-case" species representative of bioaccumulation; an important game species and assumed
to be utilized for human consumption below the Narrows Dam. Ten discrete samples (fish) will
be collected from each sampling location and submitted for PCB and dioxin congener analyses.
In addition, largemouth bass (Micropterus salmoides) and a representative sunfish species
(Lepomis sp.) will be collected, processed and shipped to the analytical lab and archived until
results of the channel catfish tissue analyses have been reviewed. The archived tissue will be
analyzed if warranted.
If the target species are not present in the sampling site, alternative species will be selected based
upon trophic level and feeding regime. Surrogate species for channel catfish may include
common carp (Cyprinus carpio), bullhead (Ameiurus sp.) or redhorse (Moxostoma sp.). If
largemouth bass are not readily collected, an alternative species such as crappie (Pomoxis sp.) or
walleye (Stizostedion vitreum) may be collected and archived. If sunfish are not present, a
representative species will be identified based upon field observations.
2.2 SAMPLING SITE SELECTION
Ten (10) individuals of each of the three target species will be collected from two sites which are
presented on Figure 2-1. These locations include the following:
1) A 0.5 mile stretch of the Yadkin River downstream of the Narrows Dam. The Study
Area is in the immediate vicinity of the Narrows Cove where previous sediment
investigations indicated detectable concentrations of PCB and dioxin congeners. The site
was expanded beyond the cove to increase the likelihood of collecting the target species
based on habitat as well as to include the main stem of the Yadkin River which is more
representative of the exposure pathway to recreational users.
2-1
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SECTIONTWO Fish Tissue Monitoring
2) The northeastern arm of Badin Lake (Background Area). This area is located up
gradient and uninfluenced by the site.
If the target species are not encountered then alternative species will be collected as discussed in
Section 2.1.1.
2.3 FIELD AND LABORATORY METHODS
2.3.1 Sampling Method
The primary fish collection device will be a boat-mounted electrofishing unit. The electrofishing
unit consists of a dual aluminum booms extending approximately 5 feet off the bow of the boat.
An umbrella array of stainless steel electrodes is attached to each boom and positioned so that it
enters the water at a depth less than 2 feet. The boom is connected with electrical cables to a
commercial electrical fish shocking unit (Smith-Root 1.5 KVA Electrofishers or equivalent),
which produces an electrical field varying from 175 volts at 1 amp to 400 volts at 6 amps. The
unit is powered by a portable gas generator. Two to three people are needed to operate the boat-
mounted electrofishing unit. One person operates the motor and steers the boat while the other
person(s) operate(s) the electrofishing unit. Fish are immobilized by the current and are
retrieved with a dip-net for processing. Channel catfish are benthic dwellers and therefore may
not be readily collected using electrofishing techniques; therefore additional passive methods
may be required for this target species.
Additional methods of collection that may be used include gill nets, hoop and fyke nets and
trotlines. Gill nets are entangling methods of collection, and high mortality may result from
these methods. Fish traps may also be utilized for fish sample collection, particularly since the
target species is a bottom dweller and the sample period is winter. Fish may be in lower water at
this time of year a more difficult to collect compared to spring and summer. The selectivity of
each method is dictated by the bait used, mesh size, and/or throat diameter of the trap.
Target fish will be measured, weighed, scaled (largemouth bass, sunfish), skinned (channel
catfish), sexed, filleted, tagged, wrapped in clean aluminum foil, placed in a plastic bag and
packed in a cooler for shipping. Filets will be taken from the fish according to approved EPA
methods (USEPA 2000). Left filets and right filets will be wrapped individually. The left filet
will be analyzed initially and right filets will be archived and potentially used for future analyses
if warranted. The minimum size requirement for the target species will be 300 mm for channel
catfish, 360 mm for largemouth and 200 mm for sunfish discrete samples. If sunfish are not of
sufficient size to yield the minimum tissue weight (100 g), then composite samples will be
processed. Composite samples will be from identical species and consist of 5 individuals within
75% of the largest to smallest specimen by total length.
All equipment used to filet and prepare samples for analysis will be decontaminated in
accordance with QA/QC procedures as detailed in Section 3.3.4. Clean knives and cutting
boards will be used for each fish processed.
2-2
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SECTIONTWO
Fish Tissue Monitoring
2.3.2 Sample Identification
The following sample identification system will be used for fish tissue samples collected during
the fish monitoring program.
SS-FS-##-QC
SS = Sample Site
BLREF = Badin Lake (Reference), and
FRMZ = Fall Reservoir, Monitoring Zone
FS = Fish Species
CCF = Channel Catfish, and
LMB = Largemouth Bass, and
SF = Sunfish (possible BG=bluegill, GSF=green sunfish, etc)
## = Sequential sample interval number for tissue samples
QC = QC designation
0 = Normal field sample,
1 = Field duplicate,
3 = MS/MSD, and
5 = Equipment blank
Fish samples will be shipped on dry ice under chain of custody via overnight carrier to Pace
Analytical located in Green Bay, Wisconsin.
2.3.3 Analytical Methodology
Polychlorinated biphenyls (PCBs) congeners and Aroclors will be analyzed using Method 1668
and SW846 Method 8082. Dioxin congeners will be analyzed by Method 1613A. Pace
Analytical located in Green Bay, Wisconsin will be the primary laboratory which will prepare
the homogenized tissue and provide Pace Analytical of Minneapolis, Minnesota an aliquot for
extraction and analysis of the dioxin and PCB congeners. The transfer of the homogenized
matrix will be under strict chain of custody procedures and documentation will be provided to
URS on the day of shipment.
Samples will be analyzed within 14 days from the date of extraction. A complete description for
these methods including extraction, lipid analysis and target analytes are included in Section 5 of
the QAPP. Laboratory standard operating procedures are included in Appendix B of the QAPP.
Only those congeners identified in sediments as identified in Section 1.1 will be included in the
final report.
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SECTIONTWO
Fish Tissue Monitoring
2.3.4 QA/QC
Three types of QA/QC samples will be collected to meet the project DQOs described in the
QAPP. QA/QC samples will be collected only for samples undergoing chemical analysis.
• Field/Equipment Rinsate Blanks
A blank prepared in the field using water provided by Pace Analytical. The water is
poured over/through sampling equipment which has been previously decontaminated.
The blank water is then collected into sample bottles and analyzed for the chemicals of
interest. The purpose of this blank is to ensure that field conditions and/or equipment are
not introducing chemicals to the samples.
• Field Duplicates
A duplicate sample prepared in the field and sent to the laboratory for analysis. The
results will provide some indication of the homogeneity of the sample medium and the
precision of the field sampling and laboratory sample analysis. Accurate field notes will
ensure that each duplicate can be matched to its corresponding investigatory sample.
• Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A `MS' is a subsample of an investigatory sample to which the laboratory adds a spike
containing analytes at known concentrations prior to extraction/analysis of the sample to
assess the effect of sample matrix on the extraction and analysis methodology. The MSD
is another subsample from the original investigatory sample (subsampling performed at
the laboratory) which is similarly spiked.
Field duplicates, MS/MSDs, and rinsate blanks will be collected at the frequency shown in the
table below for each parameter class of interest.
2.3.4.1 Decontamination Procedures
Field QA/QC procedures include decontamination of processing equipment. Sampling
equipment will be cleaned on-site prior to use for processing fish samples. The decontamination
process includes the following:
• Wash and scrub with low phosphate detergent;
• Tap water rinse;
• Deionized water rinse;
• An isopropanol rinse;

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* which ever is less
SECTIONTWO Fish Tissue Monitoring
• Deionized water rinse;
• Air dry; and
• Wrap in aluminum foil.
2.3.4.2 Sample Custody
Procedures to ensure the custody and integrity of the samples begin at the time of sampling and
continue through transport, sample receipt, preparation, analysis and storage, data generation and
reporting, and sample disposal. Field personnel shall maintain Chain of Custody records for all
field and field QC samples. All sample containers will be sealed in a manner that will prevent or
detect tampering if it occurs.
The Chain of Custody for each sample cooler will be placed in a sealable plastic bag and taped to
the inside of the sample cooler lid prior to transporting the samples to the laboratory. The
following minimum information concerning the sample shall be documented on the laboratory
Chain of Custody form:
• Unique sample identification;
• Sample type;
• Place, date, and time of sample collection;
• Number of containers/analytical fractions per sample;
• Designation of MS/MSD;
• Analyses required;
• Custody transfer signatures and dates and times of sample transfer from the field to
transporters and to the laboratory or laboratories; and
• Bill of lading or transporter tracking number (if applicable).
2.3.4.3 Sample Shipping
All sample coolers will be sealed in a way that will prevent tampering or provide direct evidence
in the event of tampering. A signed and dated custody seal will be placed on each cooler and
will then be sealed with packing tape. Address labels and shipping documentation will be
affixed to all coolers prior to shipment. Samples for the sampling event are not expected to be
classified as hazardous.
2.3.5 Derived Waste Management
Decontamination water and all solid waste (i.e., nitrile gloves, aluminum foil, plastic sheeting.)
will be handled and disposed of in accordance with the Alcoa onsite procedures. Biological
waste (fish remains) will be disposed at each of the respective sampling locations by sinking
offal s.
2-5
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Title: Fish Sampling Locations

Drawn By:
TDH
Figure 2-1
Revision Date:
10/17/07
Source:
SECTIONTHREE
Reporting and Schedule
3.1 REPORTING AND SCHEDULE
The fish sampling event will be conducted upon approval of the Work Plan. Analytical results
and data validation of the results will be completed within 60 days following completion of the
field sampling event. A draft report summarizing the field sampling activities and analytical
data will be completed within 90 days following completion of the field activities. The report of
results will include only those PCB and dioxin congeners detected in sediments as listed in
Section 1.1.

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SECTIONFOUR
References
Engineering, Inc. 2006. Investigation Summary Report. Alcoa Power Generating, Inc. - Yadkin
Division. Narrows Dam Powerhouse. Houston, Texas
USEPA. (2000). Guidance of Assessing Chemical Contaminant Data for Use in Fish Advisories.
Volume I. Fish Sampling and Analysis. Third Edition. Washingtion D.C.: Office of
Water.
L i ) ?D'
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APPENDIX A
BHE Environmental Analytical Data
SGS Environmental Services
Method 1613
S-9
BHE Environmental
Analvtical Data Rnmmnrv Cheet
Analyte Amount RL RT Ratio Qualifier
W/O (pg/g) (min.)
2,3,7,8-TCDD 21.1 1.00 31:26 0.77 Q
1,2,3,7,8-PeCDD ND 5.00
1,2,3,4,7,8-HxCDD ND 5.00
1,2,3,6,7,8-HxCDD ND 5.00
1,2,3,7,8,9-HxCDD ND 5.00
1,2,3,4,6,7,8-HpCDD 63.2 5.00 40:17 1.05
OCDD 553 10.0 44:41 0.90
2,3,7,8-TCDF 48.5 1.00 30:47 0.80 Q
1,2,3,7,8-PeCDF 5.83 5.00 33:26 1.59 Q
2,3,4,7,8-PeCDF 15.7 5.00 34:02 1.58 Q
1,2,3,4,7,8-HxCDF 8.59 5.00 36:08 1.29
1,2,3,6,7,8-HxCDF ND 5.00
2,3,4,6,7,8-HxCDF ND 5.00
1,2,3,7,8,9-HxCDF ND 5.00
1,2,3,4,6,7,8-HpCDF 22.4 5.00 39:02 1.05
1,2,3,4,7,8,9-HpCDF ND 5.00
OCDF 81.2 10.0 44:57 0.90
Total TCDDs 23.4 1.00 Q
Total PeCDDs ND 5.00 Q
Total HxCDDs 17.6 5.00
Total H CDDs 120 5.00
Total TCDFs 228 1.00 Q
Total PeCDFs 111 5.00 Q
Total HxCDFs 44.3 5.00
Total H CDFs 64.3 5.00
WHO-2005 TEQ (ND=O) 32.7
WHO-2005 TEQ ND='/z 36.8
Client Information Sample Information
Project Name: Narrows Cove
Matrix: Sediment
Sample ID: S-9 Weight / Volume: 17.45 grams
Solids / Lipids: 68.0 %
Original pH : NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176
Sample ID: G679-176-1D Filename: a17sep07a-5
Collection Date/Time: 06-Sep-07 12:47 Retchk: al7sep07a-1
Receipt Date: 08-Sep-07 10:30 Begin ConCal: a17sep07a-1
Extraction Date: 12-Sep-07
Analysis Date: 17-Sep-07 14:15 Initial Cal: m1613-071007a
1 /2
SGS Environmental Services
Method 1613
S-9
BHE Environmental
Labeled
Standard Expected
Amount
(ng) Measured
Amount
(ng) Percent
Recovery
(%) RT

(min.) Ratio Qualifier
Extraction Standards
13012-2,3,7,8-TCDD 2 1.78 89.1 31:25 0.78 Q
13C12-1,2,3,7,8-PeCDD 2 1.58 79.2 34:12 1.57
13C12-1,2,3,4,7,8-HxCDD 2 1.89 94.5 36:50 1.27
13C12-1,2,3,6,7,8-HxCDD 2 1.81 90.6 36:55 1.26
13C12-1,2,3,4,6,7,8-HpCDD 2 1.76 87.9 40:16 1.06
13C12-OCDD 4 3.11 77.8 44:40 0.90
13C12-2,3,7,8-TCDF 2 1.85 92.6 30:46 0.79 Q
13C12-1,2,3,7,8-PeCDF 2 1.57 78.4 33:26 1.59 Q
13C12-2,3,4,7,8-PeCDF 2 1.44 71.9 34:01 1.59 Q
13C12-1,2,3,4,7,8-HxCDF 2 1.81 90.6 36:07 0.52
13C12-1,2,3,6,7,8-HxCDF 2 1.77 88.3 36:13 0.53
13C12-2,3,4,6,7,8-HxCDF 2 1.79 89.3 36:43 0.53
13C12-1,2,3,7,8,9-HxCDF 2 1.76 88.1 37:30 0.53
13C12-1,2,3,4,6,7,8-HpCDF 2 1.70 84.8 39:01 0.46
13C12-1,2,3,4,7,8,9-HpCDF 2 1.61 80.4 40:56 0.45
Cleanup Standard
37C14-2,3,7,8-TCDD 0.4 0.376 94.0 31:26 Q
Iniection Standards
13C12-1,2,3,4-TCDD 2 30:53 0.79 Q
13C12-1,2,3,7,8,9-HxCDD 2 37:11 1.25
Client Information Sample Information
Project Name: Narrows Cove
Matrix: Sediment
Sample ID: S-9 Weight / Volume: 17.45 grams
Solids / Lipids: 68.0 %
Original pH : NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176
Sample ID: G679-176-1D Filename: al7sep07a-5
Collection Date/Time: 06-Sep-07 12:47 Retchk: al7sep07a-1
Receipt Date: 08-Sep-07 10:30 Begin ConCal: al7sep07a-1
Extraction Date: 12-Sep-07
Analysis Date: 17-Sep-07 14:15 Initial Cal: m1613-071007a
Analyzed by: Reviewed by:
Date: WLbol Date:
Form Version.[ 1613_HRMS 12_v5.05]Repor
2/2
TCDF Confirmation - Method 1613
S-9
BHE Environmental
Analvtical Data Summarv Sheet
Analyte Amount
(Pwg) Adj. RL
WHO RT
(min.) Ratio Qualifier
2,3,7,8-TCDF 52.8 0.843 20.60 0.80
Labeled Spiked RT Ratio Qualifier
Standard Amount
n min.
Extraction Standards
13C12-2,3,7,8-TCDF 2.00 20.59 0.79
Client Information Sample Information
Project Name: Narrows Cove Report Basis: Dry
Matrix: Sediment
Sample ID: S-9 Weight / Volume: 17.45 g
Solids / Lipids: 68.0 %
Original pH : NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176 Instrument: hrms3
Sample ID: G679-176-1D Filename: c25sep07a-11
Collection Date/Time: 09/06/07 12:47 Retchk: c25sep07a-2
Receipt Date: 09/08/07 10:30 Begin ConCal: c25sep07a-1
Extraction Date: 09/12/07
Analysis Date/Time: 09/25/07 12:56 Initial Cal: mcf-c041807a
Analyzed by: T-P Reviewed by: 01 .
Date: AA. ISO Date: o2J
SGS Environmental Services
Method 1613
5-10
BHE Environmental
Analvtieal natn Snmmarv Sheet
Analyte Amount RL RT Ratio Qualifier
(Pg/g) (Pwg) (min.)
2,3,7,8-TCDD 15.6 1.00 31:36 0.79 Q
1,2,3,7,8-PeCDD ND 5.00
1,2,3,4,7,8-HxCDD ND 5.00
1,2,3,6,7,8-HxCDD ND 5.00
1,2,3,7,8,9-HxCDD ND 5.00
1,2,3,4,6,7,8-HpCDD 35.2 5.00 40:21 1.04
OCDD 224 10.0 44:46 0.89
2,3,7,8-TCDF 37.6 1.00 30:59 0.79 Q
1,2,3,7,8-PeCDF 8.33 5.00 33:31 1.56
2,3,4,7,8-PeCDF 28.3 5.00 34:07 1.56
1,2,3,4,7,8-HxCDF 55.5 5.00 36:19 1.25
1,2,3,6,7,8-HxCDF 25.3 5.00 36:24 1.25
2,3,4,6,7,8-HxCDF 10.6 5.00 36:57 1.27
1,2,3,7,8,9-HxCDF 17.6 5.00 37:42 1.26
1,2,3,4,6,7,8-HpCDF 44.9 5.00 39:06 1.06 Q
1,2,3,4,7,8,9-HpCDF 18.3 5.00 41:01 1.06
OCDF 23.6 10.0 45:03 0.89
Total TCDDs 29.1 1.00 Q
Total PeCDDs 4.32 5.00 Q
Total HxCDDs 30.4 5.00
Total H CDDs 71.3 5.00
Total TCDFs 213 1.00 Q
Total PeCDFs 93.4 5.00 Q
Total HxCDFs 220 5.00
Total H CDFs 97.1 5.00 Q
WHO-2005 TEQ (ND=O) 40.1
WHO-2005 TEQ (ND=%) 43.3
Client Information Sample Information
Project Name: Narrows Cove
Matrix: Sediment
Sample ID: S-10 Weight / Volume: 16.95 grams
Solids / Lipids: 70.7 %
Original pH: NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176
Sample ID: G679-176-21) Filename: a17sep07a-6
Collection Date/Time: 06-Sep-07 13:10 Retchk: a17scp07a-1
Receipt Date: 08-Sep-07 10:30 Begin ConCal: a17sep07a-1
Extraction Date: 12-Sep-07
Analysis Date: 17-Sep-07 15:03 Initial Cal: m1613-071007a
1/2
SGS Environmental Services
Method 1613
5-10
BHE Environmental
Labeled
Standard Expected
Amount
(ng) Measured
Amount
(ng) Percent
Recovery
(%) RT

(min.) Ratio Qualifier
Extraction Standards
13CIZ-2,3,7,8-TCDD 2 1.90 95.1 31:35 0.78 Q
13C12-1,2,3,7,8-PeCDD 2 1.90 95.0 34:17 1.58
13C12-1,2,3,4,7,8-HxCDD 2 1.67 83.7 37:02 1.26
13C1z-1,2,3,6,7,8-HxCDD 2 1.77 88.4 37:07 1.25
13C12-1,2,3,4,6,7,8-HpCDD 2 1.77 88.6 40:20 1.05
13C12-OCDD 4 3.10 77.6 44:45 0.90
13C12-2,3,7,8-TCDF 2 1.82 91.2 30:58 0.80 Q
13C12-1,2,3,7,8-PeCDF 2 1.78 89.0 33:31 1.57
13C12-2,3,4,7,8-PeCDF 2 1.68 84.1 34:06 1.59
13CI2-1,2,3,4,7,8-HxCDF 2 1.76 87.9 36:18 0.53
13CI2-1,2,3,6,7,8-HxCDF 2 1.68 84.0 36:24 0.53
13C12-2,3,4,6,7,8-HxCDF 2 1.70 85.2 36:57 0.53
13C12-1,2,3,7,8,9-HxCDF 2 1.48 73.9 37:42 0.53
13C12-1,2,3,4,6,7,8-HpCDF 2 1.47 73.7 39:06 0.45 Q
13C12-1,2,3,4,7,8,9-HpCDF 2 1.64 82.2 40:60 0.46
Cleanup Standard
37C14-2,3,7,8-TCDD 0.4 0.395 98.7 31:36 Q
Infection Standards
13C12-1,2,3,4-TCDD 2 31:01 0.79 Q
13C12-1,2,3,7,8,9-HxCDD 2 37:24 1.25
Client Information Sample Information
Project Name: Narrows Cove
Matrix: Sediment
Sample ID: 5-10 Weight / Volume: 16.95 grams
Solids / Lipids: 70.7 %
Original pH : NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176
Sample ID: G679-176-21) Filename: aI7sep07a-6
Collection Date/Time: 06-Sep-07 13:10 Retchk: al7sep07a-1
Receipt Date: 08-Sep-07 10:30 Begin ConCal: al7sep07a-1
Extraction Date: 12-Sep-07
Analysis Date: 17-Sep-07 15:03 Initial Cal: m1613-071007a
Analyzed by: 7vP Review ed by:
Date: y4ni,o7 Date: g e
Fonn Version:[] 613_HRMS12 v5.05iReE
212
TCDF Confirmation - Method 1613
5-10
BHE Environmental
Analvtical Data Summarv Sheet
Analyte Amount
(Pwg) Adj. RL
(Pg/g) RT
(min.) Ratio Qualifier
2,3,7,8-TCDF 29.9 0.835 20.69 0.78
Labeled Spiked RT Ratio Qualifier
Standard Amount
n) (min.)
Extraction Standards
13C12-2,3,7,8-TCDF 2.00 20.67 0.80
Client Information Sample Information
Project Name: Narrows Cove Report Basis: Dry
Matrix: Sediment
Sample ID: S-10 Weight / Volume: 16.95 g
Solids / Lipids: 70.7 %
Original pH : NA
Laboratory Information Batch ID: WG14466
Project ID: G679-176 Instrument: hrms3
Sample ID: G679-176-21) Filename: c25sep07a-12
Collection Date/Time: 09/06/07 13:10 Retchk: c25sep07a-2
Receipt Date: 09/08/07 10:30 Begin ConCal: c25sep07a-1
Extraction Date: 09/12/07
Anal sis Date/Time: 09/25/07 13:20 Initial Cal: mcf-c041807a
Analyzed by: ?v*-l Reviewed by:
Date: 01.2.5 rn Date: 9 o?
PCB Congener Results by Method 1668A
Client Project ID: Client Sample ID
Narrows Cove S-9
Laboratory Information Sample Information
Lab Project ID: G679-176 Matrix: Sediment
Lab Sample ID: G679-176-1H Amount: 0.0220 g
Dilution factor: 1 pH: NA
Collection Date/Time: 06-Sep-07 12:47 Solids/Basis: 68.0 / Dry
Receipt Date/Time: 08-Sep-07 10:30 QC Batch ID: WG14471\14471
Extraction Date/Time: 14-Sep-07 Filename: bl7sep07a-10
Analysis Date/Time: 17-Sep-07 20:01 ConCal: bl7sep07a-1
RRT Std: bl7sep07a-2
Initial Cal: ml668a-b032707c
Analyte Amount EDL RT Ratio Qualifier
(Congener#) (pg/g) (pg/g) # #
81-TeCB ND 6626 U
77-TeCB 30100 7523 27:02 0.82
123-PeCB 6720 706 29:45 1.64
118-PeCB 563000 777 30:10 1.59
114-PeCB 7870 756 30:52 1.75
105-PeCB 216000 827 31:46 1.58
126-PeCB 14600 938 36:12 1.49
167-HxCB 37100 376 38:59 1.17
156,157-HxCB 95600 422 40:39 1.25
169-HxCB ND 405 U
180,193-HpCB 406000 1543 42:50 1.04
170-HpCB 213000 2067 44:42 1.04
189-H CB 6900 435 49:36 1.08
Recovery Information
Labeled Amount Measured Percent RT Ratio Qualifier
Standard Spiked Amount Recovery
n n) % # min. # #
Extraction Standards (25-150%)
13C-81-TeCB 2.00 1.82 91.2 26:17 0.79
13C-77-TeCB 2.00 1.74 87.2 27:01 0.77
13C-123-PeCB 2.00 1.82 91.2 29:42 1.68
13C-118-PeCB 2.00 1.67 83.3 30:08 1.60
13C-114-PeCB 2.00 1.77 88.5 30:51 1.57
13C-105-PeCB 2.00 1.71 85.6 31:44 1.59
13C-126-PeCB 2.00 1.85 92.4 36:09 1.60
13C-167-HxCB 2.00 1.67 83.7 38:58 1.35
13C-156,157-HxCB 4.00 3.43 85.7 40:39 1.26
13C-169-HxCB 2.00 1.71 85.6 45:37 1.29
13C-189-H CB 2.00 1.53 76.6 49:35 1.06
Cleanup Standards
13C-111-PeCB 2.00 1.95 97.5 27:07 1.57
13C-178-H CB 2.00 2.11 105 35:12 1.04
Injection Standards
13C-52-TeCB 2.00 16:07 0.78
13C-101-PeCB 2.00 23:41 1.55
13C-138-HxCB 2.00 34:30 1.25
13C-194-OcCB 2.00 52:54 0.87
Analyzed By: _me
Date: Zq-,oA1
Reviewed By:
Date:

Page 1 of 1
PCB Congener Results by Method 1668A
Client Project ID: Client Sample ID
Narrows Cove 5-10
Laboratory Information Sample Information
Lab Project ID: G679-176 Matrix: Sediment
Lab Sample ID: G679-176-2F Amount: 0.0200 g
Dilution factor: 1 pH: NA
Collection Date/Time: 06-Sep-07 13:10 Solids/Basis: 70.7 / Dry
Receipt Date/Time: 08-Sep-07 10:30 QC Batch ID: WG14471\14471
Extraction Date/Time: 14-Sep-07 Filename: bI7sep07a-11
Analysis Date/Time: 17-Sep-07 21:03 ConCal: bl7sep07a-1
RRT Std: bl7sep07a-2
Initial Cal: ml668a-b032707c
Analyte Amount EDL RT Ratio Qualifier
(Congener#) (pg/L) (pg/L) # #
81-TeCB ND 1564 U
77-TeCB 18000 1794 27:01 0.78
123-PeCB 43700 1291 29:44 1.60
118-PeCB 4520000 1337 30:09 1.59 E
114-PeCB 103000 1352 30:51 1.57
105-PeCB 1780000 1489 31:44 1.61
126-PeCB 29200 1653 36:12 1.63
167-HxCB 201000 812 38:58 1.30
156,157-HxCB 728000 994 40:38 1.25
169-HxCB ND 893 U
180,193-HpCB 775000 1431 42:48 1.04
170-HpCB 564000 1917 44:40 1.02
189-H CB 19700 1187 49:35 1.06
Recovery Information
Labeled Amount Measured Percent RT Ratio Qualifier
Standard Spiked Amount Recovery
n (n) % # min. # #
Extraction Standards (25-150%)
13C-81-TeCB 2.00 1.64 82.1 26:16 0.78
13C-77-TeCB 2.00 1.63 81.7 26:59 0.77
13C-123-PeCB 2.00 1.69 84.5 29:41 1.60
13C-118-PeCB 2.00 1.64 81.8 30:07 1.57
13C-114-PeCB 2.00 1.68 84.2 30:50 1.63
13C-105-PeCB 2.00 1.66 83.2 31:42 1.59
13C-126-PeCB 2.00 1.75 87.6 36:08 1.57
13C-167-HxCB 2.00 1.63 81.3 38:56 1.29
13C-156,157-HxCB 4.00 3.30 82.5 40:37 1.25
13C-169-HxCB 2.00 1.66 83.0 45:35 1.30
13C-189-H CB 2.00 1.48 73.8 49:32 1.06
Cleanup Standards
13C-111-PeCB 2.00 1.78 89.2 27:05 1.58
13C-178-H CB 2.00 1.97 98.5 35:10 1.07
Iniection Standards
13C-52-TeCB 2.00 16:07 0.76
13 C-101-PeCB 2.00 23:40 1.53
13 C-13 8-HxCB 2.00 34:29 1.26
13C-194-OcCB 2.00 52:52 0.89
Analyzed By: U E
Date: Z?pQr]
Reviewed By:
Date:

Page 1 of 1
APPENDIX B
Quality Assurance Project Plan
QUALITY ASSURANCE PROJECT
PLAN
NARROWS RESERVOIR
BADIN, NORTH CAROLINA
Prepared for
Alcoa, Inc.
2300 N. Wright Road
Alcoa, Tennessee 37701
December 6, 2007
Project Number: 20500252.00001
QUALITY ASSURANCE
PROJECT PLAN
NARROWS RESERVOIR
BADIN, NORTH CAROLINA
Prepared for:
Alcoa, Inc.
2300 N. Wright Road
Alcoa, Tennessee 37701

URS Corporation
1000 Corporate Centre Drive
Suite 250
Franklin, TN 37067
Project #20500252.00001
TABLE OF CONTENTS
1 Introduction .........................................................................................................................1-1
1.1 Purpose and Scope ......................................................................................................1-1
1.2 Sampling Design ......................................................................................................... 1-1
1.3 Analytical Methods ..................................................................................................... 1-1
1.4 Project Schedule .......................................................................................................... 1-2
2 Project Organization and Responsibility ..........................................................................2-1
2.1 Alcoa ...........................................................................................................................2-1
2.2 URS Corporation .........................................................................................................2-1
2.2.1 Subcontractors ...................................................................................................2-1
2.2.1.1 Analytical Laboratory .........................................................................2-1
3 Quality Program and Data Quality Objectives ................................................................3-1
3.1 Precision, Accuracy, Representativeness, Completeness, and Comparability ...... ...... 3-1
3.1.1 Precision ...................................................................................................... ...... 3-1
3.1.2 Accuracy ...................................................................................................... ...... 3 -2
3.1.3 Representativeness ...................................................................................... ...... 3-3
3.1.4 Completeness ............................................................................................... ......3-3
3.1.5 Comparability .............................................................................................. ...... 3-3
3.2 Method Detection Limits, Reporting Limits, and Instrument Calibration Requirements
for Quali ty Control ................................................................................................................. ......3-4
3.2.1 Method Detection Limits ............................................................................. ...... 3-4
3.2.2 Reporting Limits .......................................................................................... ......3-4
3.2.3 Instrument Calibration ................................................................................. ...... 3-4
3.3 Laboratory Elements of Quality Control ............................................................... ...... 3-4
3.3.1 Laboratory Control Sample ......................................................................... ...... 3-5
3.3.2 Matrix Spike/Matrix Spike Duplicate ......................................................... ...... 3-5
3.3.3 Surrogate Compounds ................................................................................. ...... 3-5
3.3.4 Retention Time Windows ............................................................................ ......3-6
3.3.5 Method Blank .............................................................................................. ......3-6
3.4 Field Collection Methods of Quality Control ....................................................... ...... 3-6
3.4.1 Equipment Blank ......................................................................................... ...... 3-6
3.4.2 Field Duplicates ........................................................................................... ...... 3-7
3.5 Quality Control Procedures ................................................................................... ......3-7
3.5.1 Holding Time Compliance .......................................................................... ...... 3-7
3.5.2 Confirmation ................................................................................................ ......3-7
3.5.3 Standard Materials ....................................................................................... ...... 3-8
3.5.4 Supplies and Consumables .......................................................................... ...... 3-8
4 Sampling Procedures ..........................................................................................................4-1
4.1 Field Sampling ............................................................................................................4-1
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TABLE OF CONTENTS
4. 1.1 Sample Containers .............................................................................................4-1
4.1.2 Sampling Volumes and Preservation Requirements, Holding Times ...............4-1
4.2 Sampling Handling and Custody ................................................................................4-1
5 Definitive Data Analytical Methods and Procedures ......................................................5-1
5.1 Preparation Methods ................................................................................................... 5-1
Method SW-3540C - Soxhlet Extraction .................................................................... 5-1
5.2 Analytical Methods .....................................................................................................5-1
5.3 Laboratory Data Qualifiers ......................................................................................... 5-9
6 Data Reduction, Review, Verification, Reporting, Validation and Recordkeeping ..... 6-1
6.1 Data Review, Validation, and Reporting Requirements for Definitive Data .............. 6-1
6.2 Quality Assurance Reports .......................................................................................... 6-5
6.3 Hard Copy Data Reports and Archiving ..................................................................... 6-5
6.4 Project Data Flow and Transfer .................................................................................. 6-5
6.5 Recordkeeping ............................................................................................................ 6-5
7 Project Audits and Training ..............................................................................................7-1
7.1 Project Audits ..............................................................................................................7-1
7.2 Training .......................................................................................................................7-1
8 Corrective Actions ..............................................................................................................8-1
9 References ............................................................................................................................9-1
LIST OF TABLES
Table 3-1 - Statistical Calculations
Table 5-1 - Extraction Procedures
Table 5-2 - Analytical Procedures
Table 5-3 - Detection Limits
Table 5-4 - Quality Control Limits
Table 5-5 - Laboratory Data Qualifiers
Table 6-1 - Validation Data Qualifiers
Table 6-2 - General Validation Flagging Conventions
Table 6-3 - Validation Flagging Conventions for Organic Methods
APPENDICES
Appendix A - Pace Analytical SOPS and Quantitative Limits
EM
QAPP.doc
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ii
SECTIONONE Introduction
Alcoa's Badin Works is located on Highway 740 in Badin, Stanly County, North Carolina (Figure 1-1).
The Badin Works occupies 123 acres of land and the fenced, active part of the site is about 90 acres. In
addition, Alcoa Power Generating Inc. (APGI), a wholly-owned subsidiary of Alcoa Inc. (Alcoa)
operates four hydroelectric developments, the High Rock, Tuckertown, Narrows and Falls
developments, which are located on a 38-mile stretch of the Yadkin River. Narrows was the first
of the Project developments to be built, and was completed in 1917. Narrow's Dam consists of a
main dam section and a bypass spillway section.
In September 2007, BHE Environmental was contracted by Alcoa to collect sediment samples
from the cove which is adjacent to the area where elevated levels of PCBs and dioxins were
detected in soils. BHE Environmental collected two sediment samples which were subsequently
analyzed for select PCB congeners, dioxin and furans. The data indicated that sediments also
contained detectable levels of PCBs and dioxins. In cooperation with the State of North
Carolina, Alcoa contracted URS Corporation to prepare a Work Plan detailing the procedures for
obtaining fish samples to evaluate if PCBs and dioxins are detectable in biological tissue
immediately below the Narrow's Dam.
1.1 PURPOSE AND SCOPE
The objectives of the proposed fish tissue sampling event are to:
1. Determine if PCB congeners and Aroclors and dioxins congeners are detectable in fish
tissue collected adjacent to the Narrow's Cove; and
2. If PCBs and dioxin are detected in fish tissue samples, are the concentrations comparable
to levels detected in tissues collected from the representative reference area.
1.2 SAMPLING DESIGN
A description of the sampling design can be found in Sections 2.0 of the Work Plan.
1.3 ANALYTICAL METHODS
The analytical methods for this field investigation are presented in the following table (Table 1-
4
Table 5-. Analytical Methods
Analytical Method Analytes
Method 1613 Dioxin Congeners
Method 1668 PCB Congeners
SW-846 Method 8082 PCB Aroclors
1-1
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SECTIONONE
Introduction
1.4 PROJECT SCHEDULE
The fish sampling event can be conducted upon approval of the Work Plan and receipt of the
Scientific Collection permit as required by the State of North Carolina. The initial sampling
event will tentatively be completed in December 2007.
Analytical results and data validation of the results will be completed within 45 days following
completion of the field sampling event. The draft report summarizing the field sampling
activities and analytical data will be completed within 60 days following completion of the field
activities Project Organization and Responsibility
UM 1-2
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SECTIONTWO Project Organization and Responsibility
The Project Team for the MNRPP will consist of the following:
• Alcoa.
• URS Corporation (MNRPP Consultant);
• Relevant Subcontractors.
The role of each of these entities is discussed in the following sections.
2.1 ALCOA
Overall administrative control of the M?yRPP will be the responsibility of the Alcoa Project
Manager, Mr. Robert Prezbindowski. He will be the only point of contact between Alcoa and
the regulatory agency. In addition, he will act as the primary point of client contact for URS
Corporation. In this role, he will be responsible for final approval of the Work Plan and
technical and administrative procedures, as well as ensuring that the necessary arrangements are
made to facilitate implementation of the fish sampling activities.
2.2 URS CORPORATION
The Consultant will be URS Corporation (URS), who will perform the investigative activities
and will be responsible for the execution of the Work Plan.
The URS Project Manager will be Mr. Todd D. Hunt, who will oversee the implementation of
the project through the field investigation stages. He will directly manage budgets and project
milestones, as well as be the main point of contact with Alcoa during field activities. URS
QA/QC Manager in charge of data validation will be Mr. Peter Ciarleglio, Senior Chemist.
2.2.1 Subcontractors
Subcontractors will report directly to the URS Project Manager and will be responsible for
ensuring that all equipment and procedures are in accordance with established standards.
2.2.1.1 Analytical Laboratory
Polychlorinated biphenyls (PCBs) congeners and Aroclors will be analyzed using Method 1668
and SW846 Method 8082. Dioxin congeners will be analyzed by Method 1613A. Pace
Analytical located in Green Bay, Wisconsin will be the primary laboratory facility which will
prepare the homogenized tissue and provide Pace Analytical of Minneapolis, Minnesota an
aliquot for extraction and analysis of the dioxin and PCB congeners. The transfer of the
homogenized matrix will be under strict chain of custody procedures and documentation will be
provided to URS on the day of shipment.
Analytical laboratory testing for this project will be under direct contract with URS Corporation
and the URS Project Manager will handle all coordination duties. Tod Noltemeyer will serve as
the Laboratory Project Manager (LPM) for the project as well as the coordinator between the
primary and secondary locations.
2-1
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SECTIONTHREE Quality Program and Data Quality Objectives
The LPM will be the liaison to URS Project Manager, personnel and laboratory staff. In
addition, the LPM will assign specific duties for this project to the laboratory staff and provide
orientation of the staff to project-specific Quality Assurance/Quality Control (QA/QC) needs and
requirements. The LPM will also ensure that laboratory-specific procedures and internally
prepared plans and reports meet project QA requirements. The LPM will serve as the liaison
between the laboratory project staff and other internal or external organizations, and will also
ensure that the laboratory's performance meets the requirement of the project's contract.
Data Quality Objectives (DQOs) specify the data type, quality, quantity, and uses needed to
make decisions and are the basis for designing data collection activities.
3.1 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND
COMPARABILITY
Data quality elements include precision, accuracy, representativeness, completeness, and
comparability. The basis for assessing each of these elements of data quality is discussed in the
following sections. Precision and accuracy QC limits for each method and matrix are identified
in Section 5.0.
3.1.1 Precision
Precision measures the reproducibility of measurements. It is strictly defined as the degree of
mutual agreement among independent measurements as the result of repeated application of the
same process under similar conditions.
Analytical precision is the measurement of the variability associated with duplicate (two) or
replicate (more than two) analyses. This is accomplished in the laboratory by calculating the
RPD between lab duplicate samples, or the RPD between laboratory generated MS/MSD
samples.
The laboratory control sample (LCS) is used to determine the precision of the analytical method.
If the recoveries of analytes in the LCS are within established control limits (CLs), then precision
is within limits. In this case, the comparison is not between a sample and a duplicate sample
analyzed in the same batch, rather the comparison is between the sample and samples analyzed
in previous batches.
Total precision is the measurement of the variability associated with the entire sampling and
analysis process. It is determined by analysis of duplicate or replicate field samples and measures
variability introduced by both the laboratory and field operations. Field duplicate samples and
matrix duplicate spiked samples are analyzed to assess field and analytical precision, and the
precision measurement is determined using the relative percent difference (RPD) between the
duplicate sample results. The formula for the calculation of precision is provided in Table 3-1 as
RPD. For replicate analyses, the relative standard deviation (RSD) is determined. The formula
for the calculation of RSD is provided in Table 3-1. The required level of precision differs
according to the method, and is designated in the accuracy and precision tables or text in Section
5.0.
3-1
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SECTIONTHREE Quality Program and Data Quality Objectives
3.1.2 Accuracy
Accuracy is a statistical measurement of correctness and includes components of random error
(variability due to imprecision) and systemic error. It therefore reflects the total error associated
with a measurement. A measurement is accurate when the value reported does not fall outside of
established Control Limits (CL) around the true value or known concentration of the spike or
standard. Sample matrix accuracy is determined by comparing the percent recovery of analytes
spiked into actual samples as a matrix spike, or matrix spike duplicate (MS/MSD) to a control
limit. Analytical method accuracy is measured by comparing the percent recovery of analytes
spiked into an LCS of the same matrix as the samples, to a CL. Analysis of performance
evaluation (PE) samples is also used to provide additional information for assessing the accuracy
of the analytical data being produced. The laboratory may be required to periodically analyze or
produce results from an unknown PE sample of the same matrix as the samples for this project.
Both accuracy and precision are calculated and the associated sample results are interpreted by
considering these specific measurements. The formula for calculation of accuracy is included in
Table 3-1 as percent recovery (%R) from pure and sample matrices. Accuracy requirements are
listed for each method in Section 5.0.
TABLE 3-1
STATISTICAL CALCULATIONS
Statistic Symbol Formula Definition Uses

Mean

X n
x,
Measure of central
Used to determine average
=r tendency value of measurements
n

Standard z
(x
- X)
Meas
re of relati
e
Used in calc
latin
S , u
v g
u
Deviation (n _ 1) scatter of the data variation of measurements

Relative Relative standard
Used to assess precision for
Standard RSD (S / X) x 100 deviation, adjusts for replicate results, calibration
Devaition magnitude of response factors
observations

Percent
%D
x1 ? X2 x 100 Measure of the
difference of two
Used to assess acceptability
Difference x, observations of continuing calibration
Relative (X X2 Q
' - z
100 Measure of variability Used to assess total and
Percent RPD x
(X X )/2)
+ that adjusts for the
i
f
d analytical precision of
Difference z
' magn
tu
e o duplicate measurements
observations
Percent
O X
X e X100 Recovery of spiked
compound in sample Used to assess matrix
Recovery
true
matrix effects and total accuracy
Correlation R see SW-8000B section Evaluation of "goodness of
Coefficient 7.5.3 fif' of a regression line
Coefficient of see SW-8000B section Evaluation of "goodness of
Determination COD 7 5 3 fif' of a polynomial
equation
x = Observation (concentration)
n = Number of observations
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SECTIONTHREE Quality Program and Data Quality Objectives
3.1.3 Representativeness
Objectives for representativeness are defined for each sampling and analysis task and are a
function of the investigative objectives. Representativeness is achieved through use of the
standard field, sampling, and analytical procedures. Representativeness is determined by
appropriate program design, with consideration of elements such as proper sampling locations,
procedures, and target species. Decisions regarding sample locations and the statistical sampling
design are documented in Section 3.3 of the Work Plan.
3.1.4 Completeness
Completeness is calculated for the aggregation of data for each analytical group measured for
any particular sampling event or other defined set of samples (e.g., by site). Completeness is
calculated and reported for each analytical method or group (i.e., Methods 1668a and 1613) and
sample matrix (i.e., fish tissue). The number of valid results divided by the number of possible
individual analyte results, expressed as a percentage, determines the completeness of the data set.
For completeness requirements, valid results are all results not qualified with an "R" flag (see
Section 6.0 for an explanation of validation flagging criteria). For any instances of samples that
could not be analyzed for any reason (holding time violations in which resampling and analysis
were not possible, spoiled samples, etc.), the numerator of this calculation becomes the number
of possible results minus the number of possible results not reported. The formula for calculation
of completeness is presented below:
/o o number of valid (i.e.,: non - R flagged) results
completeness = x 100
number of possible results
3.1.5 Comparability
Comparability is the confidence with which one data set can be compared to another data set.
The objective for this QA/QC program is to produce data with the greatest possible degree of
comparability. The number of matrices that are sampled and the range of field conditions
encountered are considered in determining comparability. Comparability is achieved by using
standard methods for sampling and analysis, reporting data in standard units, normalizing results
to standard conditions, and using standard and comprehensive reporting formats. Complete field
documentation using standardized data collection forms will support the assessment of
comparability. Analysis of PE samples and reports from audits will also be used to provide
additional information for assessing the comparability of analytical data produced among
subcontracting laboratories. Historical comparability will be achieved through consistent use of
methods and documentation procedures throughout the project.
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SECTIONTHREE Quality Program and Data Quality Objectives
3.2 METHOD DETECTION LIMITS, REPORTING LIMITS, AND INSTRUMENT
CALIBRATION REQUIREMENTS FOR QUALITY CONTROL
3.2.1 Method Detection Limits
The method detection limit (MDL) is the minimum concentration of a substance that can be
measured and reported with 99% confidence that the analyte concentration is greater than zero.
The laboratory will establish MDLs for each method and analyte for every instrument the
laboratory plans to use for the project. The laboratory will revalidate these MDLs at least once
per twelve month period. The laboratory will provide the MDL demonstrations both at the
beginning of the project (i.e., before project samples are analyzed) and upon request. Results less
than or equal to the MDL will be reported as the MDL value and flagged with a "U" (see Section
5.0).
Laboratories participating in this work effort will demonstrate the MDLs for each instrument,
including confirmatory columns, method of analysis, analyte, and matrix (i.e., biota) using 40
CFR Part 136 Appendix B.
3.2.2 Reporting Limits
The laboratories participating in this work effort shall compare the results of the MDL
demonstrations to the reporting limits (RLs) for each method that is listed in Section 5.0. The
MDL may not be more than one-half the corresponding RL. For organic analyses, the
laboratories shall also verify RLs by including a standard at or below the RL as the lowest point
on the calibration curve. All results shall be reported at or above the MDL values; however, for
those results falling between the MDL and the RL, a "J" flag shall be applied to the results,
indicating that such values are estimated (see Section 5.0). No results shall be reported below the
MDL.
3.2.3 Instrument Calibration
Analytical instruments will be calibrated in accordance with the analytical methods. All analytes
reported will be present in the initial and continuing calibrations, and these calibrations will meet
the acceptance criteria specified in Section 5.0. All calibration criteria will satisfy Methods 1668
and 1613 at a minimum. Multipoint calibrations will contain the minimum number of calibration
points specified in the method with all points used for the calibration being contiguous. The only
exception to this rule is that a standard that has been statistically determined as being an outlier
can be dropped from the calibration, providing any method requirement for a minimum number
of standards is met.
3.3 LABORATORY ELEMENTS OF QUALITY CONTROL
This section presents QC requirements relevant to analysis of samples that will be followed
during all analytical activities laboratories producing definitive data. The purpose of this QC
program is to produce data of known quality that satisfy the project objectives and that meet or
exceed the requirements of the standard methods of analysis. This program provides a
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mechanism for ongoing control and evaluation of data quality measurements through the use of
QC materials.
Adequate tissue will be provided for laboratory control samples to be analyzed. The type of QC
samples and the frequency of use of these samples are discussed below and in the method-
specific subsections of Section 5.0.
3.3.1 Laboratory Control Sample
The LCS will in general be spiked with representative analytes being reported for the method, at
a level less than or equal to the midpoint of the calibration curve for each analyte. (The midpoint
is defined as the median point in the curve, not the middle of the range). The LCS will be spiked
in accordance with SOPS included in Appendix A. The LCS will be carried through the
complete sample preparation and analysis procedure.
The performance of the LCS will be evaluated against the QC acceptance limits given in the
tables in Appendix A. Whenever an analyte in an LCS is outside the acceptance limit, corrective
action will be performed. After the system problems have been resolved and system control has
been reestablished, all samples will be reanalyzed for the out-of-control analyte. When an
analyte in an LCS exceeds the upper control limit (UCL) or lower control limit (LCL) and no
corrective action is performed or the corrective action was ineffective, the appropriate validation
flag, as described in Sections 6.0, will be applied to all affected results during data validation.
3.3.2 Matrix Spike/Matrix Spike Duplicate
An MS and MSD is an aliquot of sample spiked with known concentrations of surrogate analytes
as specified in each analytical method. The spiking occurs prior to sample preparation and
analysis. Each analyte in the MS and MSD will be spiked at a level less than or equal to the
midpoint of the calibration curve for each analyte.
The MS/MSD is used to document the bias of a method due to sample matrix. Thus, for biota
samples, laboratories will use the same filet for the parent sample, the MS sample, and the MSD
sample, if sufficient volume/weight exists. The laboratory will select the samples for MS/MSDs
randomly. MS/MSD results are used to document potential matrix effects associated with a site.
The MS/MSD results and flags will be associated or related to samples that are collected from
the same site from which the MS/MSD set was collected. One MS/MSD analysis will be
performed for every twenty tissue samples (or 5%), or part thereof.
The performance of the MS and MSD is evaluated against the QC acceptance limits given in the
tables in Section 5.0. If either the MS or the MSD is outside the QC acceptance limits, the
analytes in all related samples will be qualified according to the data flagging criteria in Sections
6.0 during data validation.
3.3.3 Surrogate Compounds
The lab will add surrogate compounds as appropriate for Method 8082 to each sample prior to
extraction, to monitor recovery efficiency throughout the analytical process. Surrogates must
meet method criteria, or else corrective action is required by the lab. Specific criteria are
provided in Section 6 for the analyses to be used for this project.
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SECTIONTHREE Quality Program and Data Quality Objectives
3.3.4 Retention Time Windows
Retention time windows are used in GC and high-performance liquid chromatography (HPLC)
analysis for qualitative identification of analytes. They are calculated from replicate analyses of a
standard on multiple days. The procedure and calculation method are given in SW-846 Methods
8000B and 8082 (USEPA 1996).
When the retention time is outside of the acceptance limits, corrective action will be performed.
After the system problems have been resolved and system control has been reestablished, all
samples will be reanalyzed since the last acceptable retention time check. If corrective actions
are not performed, the appropriate validation flag, as described in Sections 6.0, will be applied to
the sample results during data validation.
3.3.5 Method Blank
A method blank is an analyte-free matrix to which all reagents are added in the same volumes or
proportions as used in sample processing. The method blank is carried through the complete
sample preparation and analytical procedure. The method blank is used to document
contamination resulting from the analytical process. A method blank will be included in every
analysis batch.
The presence of analytes in a method blank at concentrations equal to or greater than the RL
indicates a need for corrective action. Corrective action will be performed to eliminate the source
of contamination prior to proceeding with analysis. After the source of contamination has been
eliminated, all samples containing the analyte found in the method blank above the RL will be
reprepared and reanalyzed. No analytical data will be corrected for the presence of analytes in
blanks. When an analyte is detected above the MDL in the method blank and in the associated
samples and corrective actions (for samples above the RL) are not performed or are ineffective,
the laboratory will apply the appropriate qualifier (Section 5), and the appropriate validation flag,
as described in Section 6.0, will be applied to the sample results during data validation.
3.4 FIELD COLLECTION METHODS OF QUALITY CONTROL
3.4.1 Equipment Blank
Equipment blanks are used to assess the effectiveness of equipment decontamination procedures.
An equipment blank is a sample of ASTM Type II reagent grade water poured into or over the
sampling device, collected in a sample container, and transported to the laboratory for analysis.
The frequency of collection for equipment blanks is 1 per week or 1 per 20 samples/ matrix,
whichever is less, as specified in Subsection 2.3.4 of the Work Plan. Equipment blanks will be
collected immediately after the equipment has been decontaminated. Equipment blanks will be
collected in sample containers appropriate for an aqueous matrix, and preserved in accordance to
the pertinent analytical method. The blank will be analyzed for all laboratory analyses requested
for the environmental samples collected at the site.
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SECTIONTHREE Quality Program and Data Quality Objectives
When an analyte is detected in the equipment blank the appropriate validation flag, as described
in Section 6.0, may be applied to sample results from samples collected with the affected
equipment, based on professional judgment during the validation process.
3.4.2 Field Duplicates
A field duplicate sample is a second sample collected at the same location as the original sample.
Duplicate samples are collected simultaneously or in immediate succession, using identical
recovery techniques, and treated in an identical manner during storage, transportation, and
analysis. The sample containers are assigned a unique identification number in the field.
Duplicate samples will be designated based on recovered tissue volume sufficient to run two
analyses on one fillet will be submitted. Duplicate sample results are used to assess precision of
the sample collection process. The frequency of collection for field duplicates will be 10%.
Field duplicates with quantifiable results that exceed the QC criteria will be flagged as indicated
in Section 6.0
3.5 QUALITY CONTROL PROCEDURES
3.5.1 Holding Time Compliance
Sample preparation and analysis will be completed within the method-required holding times.
The holding time for a sample begins at the time of sample collection. The preparation holding
time is calculated from the time of sample collection to the time of completion of the sample
preparation process as described in the applicable method, prior to any necessary extract cleanup
and/or volume reduction procedures. If no preparation (e.g., extraction) is required, the analysis
holding time is calculated from the time of sample collection to the time of completion of all
analytical runs, including dilutions, second column confirmations, and any required reanalyses.
In methods requiring sample preparation prior to analysis, the analysis holding time is calculated
from the time of preparation completion to the time of completion of all analytical runs,
including dilutions, second column confirmations, and any required reanalyses.
If holding times are exceeded and the analyses are performed, the results will be flagged during
validation according to the procedures described in Section 6.0. Holding time variances will also
be discussed in the lab case narrative supplied with the data package.
3.5.2 Confirmation
Quantitative and qualitative confirmation of results at or above the RL for samples analyzed by
GC will be completed within the method-required holding times. For GC methods, a second
column will be used for confirmation, at least for all positive results. The only exception would
be for Method 8082 PCB analysis, and then only if one Aroclor is present and the pattern can be
clearly recognized. The result from the primary column/detector is the result that will be
reported.
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SECTIONTHREE Quality Program and Data Quality Objectives
3.5.3 Standard Materials
Standard materials, including second source materials, used in calibration and to prepare samples
will be those normally used by the analytical laboratory. The laboratory, however, is responsible
for maintaining standard accuracy and traceability in accordance with good laboratory practice.
The standard materials will be current, and the lab will insure that all expiration dates are current
for all standard materials. Expired standard materials shall be either revalidated prior to use or
discarded. Revalidation may be performed through assignment of a true value and error window
statistically derived from replicate analyses of the material as compared to an unexpired
standard. The laboratory shall label standard and QC materials with expiration dates.
A second source standard will be used to independently confirm initial calibration. A second
source standard is a standard purchased from a different vendor than the vendor supplying the
material used in the initial calibration standards. The second source material will be used for the
continuing calibration standards or for the LCS.
3.5.4 Supplies and Consumables
The laboratory will inspect supplies and consumables prior to their use in analysis. The materials
description in the methods of analysis will be used as a guideline for establishing the acceptance
criteria for these materials. Purity of reagents will be monitored by analysis of LCSs. An
inventory and storage system for these materials will ensure use before manufacturers' expiration
dates and storage under safe and chemically compatible conditions.
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SECTIONFOUR Sampling Procedures
4.1 FIELD SAMPLING
The field sampling procedures for collecting samples and sampling methods are included in
Section 2.0 of the Work Plan.
4.1.1 Sample Containers
Fish tissue samples will be wrapped in aluminum foil, and sealed inside plastic bags for shipment
to the lab.
4.1.2 Sampling Volumes and Preservation Requirements, Holding Times
This QAPP only addresses the analysis fish tissue for PCB congeners and Aroclors by Methods
SW-846 8082 and 1668, respectively. Dioxin congeners will be analyzed using Method 1613.
The sampler shall attempt to obtain at least 100 grams of fish fillets for each sample collected.
This will be sufficient filet material for the lab to perform multiple analyses, if required. All fish
are to be packaged as indicated below, and placed on ice in a cooler so as to maintain the
temperature at 2-6 degrees centigrade until the samples arrive at the lab. Samples will be frozen
upon receipt at the lab, and extraction holding time shall not exceed one year. Analysis holding
time after extraction shall not exceed 40 days.
4.2 SAMPLING HANDLING AND CUSTODY
Procedures to ensure the custody and integrity of the samples will begin at the time of sampling
and continue through transport, sample receipt, preparation, analysis and storage, data generation
and reporting, and sample disposal. Records concerning the custody and condition of the samples
will be maintained in field and laboratory records.
URS will maintain Chain-of-custody (COC) records for all field and field QC samples. A sample
is defined as being under a person's custody if any of the following conditions exist: (1) it is in
their possession, (2) it is in their view, after being in their possession, (3) it was in their
possession and they locked it up or (4) it is in a designated secure area.
The following information concerning the sample will be documented on the COC:
• Unique sample identification for each container
• Date and time of sample collection
• Source of sample (including name, location, and sample type)
• Preservative used
• Analyses required
• Name of collector
• Custody transfer signatures and dates and times of sample transfer from the field to
transporters and to the laboratory or laboratories
• Bill of lading or transporter tracking number (if applicable)
All samples will be uniquely identified, labeled, and documented in the field at the time of
collection in accordance with Subsection 2.3.2 of the Work Plan.
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SECTIONFOUR Sampling Procedures
Samples collected in the field will be transported to the laboratory or field testing site as
expeditiously as possible. The samples will be packed in ice or chemical refrigerant to keep them
cool during collection and transportation. During transit, it is not always possible to rigorously
control the temperature of the samples. As a general rule, storage at low temperature is the best
way to preserve most samples. A temperature blank (a VOC sampling vial filled with tap water)
will be included in every cooler and used to determine the internal temperature of the cooler
upon receipt of the cooler at the laboratory. If the temperature of the samples upon receipt
exceeds the temperature requirements, the exceedance will be documented in laboratory records
and discussed with URS. The decision regarding the potentially affected samples will also be
documented.
Once the samples reach the laboratory, they will be checked against information on the COC
form for anomalies. The condition, temperature, and appropriate preservation of samples will be
checked and documented on the COC form. The occurrence of any anomalies in the received
samples and their resolution will be documented in laboratory records. All sample information
will then be entered into a tracking system, and unique analytical sample identifiers will be
assigned. A copy of this information will be reviewed by the laboratory for accuracy. Sample
holding time tracking begins with the collection of samples and continues until the analysis is
complete. Samples not preserved or analyzed in accordance with these requirements will be
resampled and analyzed.
Procedures ensuring internal laboratory COC will also be implemented and documented by the
laboratory. Specific instructions concerning the analysis specified for each sample will be
communicated to the analysts. Analytical batches will be created, and laboratory QC samples
will be introduced into each batch.
While in custody of the laboratory, samples will be stored in a limited-access, temperature-
controlled areas. Refrigerators, coolers, and freezers will be monitored for temperature 7
days/week. The fish tissues will be frozen on receipt at the laboratory. The acceptance criterion
for the temperatures of the freezers is less than 0°C. All cold storage areas will be monitored by
thermometers that have been calibrated with a NIST-traceable thermometer. As indicated by the
findings of the calibration, correction factors will be applied to each thermometer. Records that
include acceptance criteria will be maintained. Samples for volatile organics determination will
be stored separately from other samples, standards, and sample extracts. Samples will be stored
after analysis until disposed of in accordance with applicable local, state, and federal regulations.
Disposal records will be maintained by the laboratory.
SOPS describing sample control and custody will be maintained by the laboratory. Copies of the
SOPS provided by Pace Analytical, Inc are included in Appendix A.
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SECTIONFIVE
Analytical Methods and Procedures
Section 5.1 briefly describes the preparation methods. Section 5.2 contains subsections for each
analytical procedure. Each subsection contains the following information:
5.1 PREPARATION METHODS
Extraction and digestion procedures for biota matrices for Methods 1668 and 1613 are part of the
Analytical Method, and are presented in the SOPS for these methods included in Appendix A.
Extraction and digestion procedures for the Method 8082 biota matrices presented in this section
are outlined in Table 5-1.
TABLE 5-1
EXTRACTION AND DIGESTION PROCED URES
Method Parameter
SW-3540C Soxhlet extraction.
Method SW-3540C - Soxhlet Extraction
Method SW-3540C will be used to extract the PCBs from biota tissue for the Method 8082
analyses. Method SW-3540C is an automated Soxhlet extraction. The Soxhlet extraction process
ensures intimate contact of the sample matrix with the extraction solvent.
5.2 ANALYTICAL METHODS
Polychlorinated biphenyls (PCBs) congeners and Aroclors will be analyzed using Method 1668
and SW-846 Method 8082, respectively. Dioxins will be analyzed using Method 1613. The
following tables present the PCB congeners and/or Aroclors which will be reported by the
analytical laboratories (Table 5-1).
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2-MoCB 1 2051-60-7
3-MoCB 2 2051-61-8
4-MoCB 3 2051-62-9
2,2'-DiCB 4 13029-08-8
2,3-DiCB 5 16605-91-7
2,3'-DiCB 6 25569-80-6
2,4-DiCB 7 33284-50-3
2,4'-DiCB 8 34883-43-7
2,5-DiCB 9 34883-39-1
2,6-DiCB 10 33146-45-1
3,3'-DiCB 11 2050-67-1
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
3,4-DiCB 12 2974-92-7
3,4'-DiCB 13 2974-90-5
3,5-DiCB 14 34883-41-5
4,4'-DiCB 15 2050-68-2
2,2',3-TrCB 16 38444-78-9
2,2',4-TrCB 17 37680-66-3
2,2',5-TrCB 18 37680-65-2
2,2',6-TrCB 19 3 8444-73 -4
2,3,3'-TrCB 20 38444-84-7
2,3,4-TrCB 21 55702-46-0
2,3,4'-TrCB 22 38444-85-8
2,3,5-TrCB 23 55720-44-0
2,3,6-TrCB 24 55702-45-9
2,3',4-TrCB 25 55712-37-3
2,3',5-TrCB 26 38444-81-4
2,3',6-TrCB 27 38444-76-7
2,4,4'-TrCB 28 7012-37-5
2,4,5-TrCB 29 15862-07-4
2,4,6-TrCB 30 35693-92-6
2,4',5-TrCB 31 16606-02-3
2,4',6-TrCB 32 38444-77-8
2',3,4-TrCB 33 38444-86-9
2',3,5-TrCB 34 37680-68-5
3,3',4-TrCB 35 37680-69-6
3,3',5-TrCB 36 38444-87-0
3,4,4'-TrCB 37 38444-90-5
3,4,5-TrCB 38 53555-66-1
3,4',5-TrCB 39 38444-88-1
2,2',3,3'-TeCB 40 38444-93-8
2,2',3,4-TeCB 41 52663-59-9
2,2',3,4'-TeCB 42 36559-22-5
2,2',3,5-TeCB 43 70362-46-8
2,2',3,5'-TeCB 44 41464-39-5
2,2',3,6-TeCB 45 70362-45-7
2,2',3,6'-TeCB 46 41464-47-5
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2,2',4,4'-TeCB 47 2437-79-8
2,2',4,5-TeCB 48 70362-47-9
2,2',4,5'-TeCB 49 41464-40-8
2,2',4,6-TeCB 50 62796-65-0
2,2',4,6'-TeCB 51 68194-04-7
2,2',5,5'-TeCB 52 35693-99-3
2,2',5,6'-TeCB 53 41464-41-9
2,2',6,6'-TeCB 54 15968-05-5
2,3,3',4'-TeCB 55 74338-24-2
2,3,3',4'-TeCB 56 41464-43-1
2,3,3',5-TeCB 57 70424-67-8
2,3,3',5'-TeCB 58 41464-49-7
2,3,3',6-TeCB 59 74472-33-6
2,3,4,4'-TeCB 60 33025-41-1
2,3,4,5-TeCB 61 33284-53-6
2,3,4,6-TeCB 62 54230-22-7
2,3,4',5-TeCB 63 74472-34-7
2,3,4',6-TeCB 64 52663-58-8
2,3,5,6-TeCB 65 33284-54-7
2,3',4,4'-TeCB 66 32598-10-0
2,3',4,5-TeCB 67 73575-53-8
2,3',4,5'-TeCB 68 73575-52-7
2,3',4,6-TeCB 69 60233-24-1
2,3',4',5-TeCB 70 32598-11-1
2,3',4',6-TeCB 71 41464-46-4
2,3',5,5'-TeCB 72 41464-42-0
2,3',5',6-TeCB 73 74338-23-1
2,4,4',5-TeCB 74 32690-93-0
2,4,4',6-TeCB 75 32598-12-2
2',3,4,5-TeCB 76 70362-48-0
3,3',4,4'-TeCB 77 32598-13-3
3,3',4,5-TeCB 78 70362-49-1
3,3',4,5'-TeCB 79 41464-48-6
3,3',5,5'-TeCB 80 33284-52-5
3,4,4',5-TeCB 81 70362-50-4
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2,2',3,3',4-PeCB 82 52663-62-4
2,2',3,3',5-PeCB 83 60145-20-2
2,2',3,3',6-PeCB 84 52663-60-2
2,2',3,4,4'-PeCB 85 65510-45-4
2,2',3,4,5-PeCB 86 55312-69-1
2,2',3,4,5'-PeCB 87 38380-02-8
2,2',3,4,6-PeCB 88 55215-17-3
2,2',3,4,6'-PeCB 89 73575-57-2
2,2',3,4',5-PeCB 90 68194-07-0
2,2',3,4',6-PeCB 91 68194-05-8
2,2',3,5,5'-PeCB 92 52663-61-3
2,2',3,5,6-PeCB 93 73575-56-1
2,2',3,5,6'-PeCB 94 73575-55-0
2,2',3,5',6-PeCB 95 38379-99-6
2,2',3,6,6'-PeCB 96 73575-54-9
2,2',3',4,5-PeCB 97 41464-51-1
2,2',3',4,6-PeCB 98 60233-25-2
2,2',4,4',5-PeCB 99 38380-01-7
2,2',4,4',6-PeCB 100 39485-83-1
2,2',4,5,5'-PeCB 101 37680-73-2
2,2',4,5,6'-PeCB 102 68194-06-9
2,2',4,5,'6-PeCB 103 60145-21-3
2,2',4,6,6'-PeCB 104 56558-16-8
2,3,3',4,4'-PeCB 105 32598-14-4
2,3,3',4,5-PeCB 106 70424-69-0
2,3,3',4',5-PeCB 107 70424-68-9
2,3,3',4,5'-PeCB 108 70362-41-3
2,3,3',4,6-PeCB 109 74472-35-8
2,3,3',4',6-PeCB 110 38380-03-9
2,3,3',5,5'-PeCB 111 39635-32-0
2,3,3',5,6-PeCB 112 74472-36-9
2,3,3',5',6-PeCB 113 68194-10-5
2,3,4,4',5-PeCB 114 74472-37-0
2,3,4,4',6-PeCB 115 74472-38-1
2,3,4,5,6-PeCB 116 18259-05-7
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2,3,4',5,6-PeCB 117 68194-11-6
2,3',4,4',5-PeCB 118 31508-00-6
2,3',4,4',6-PeCB 119 56558-17-9
2,3',4,5,5'-PeCB 120 68194-12-7
2,3',4,5,'6-PeCB 121 56558-18-0
2',3,3',4,5-PeCB 122 76842-07-4
2',3,4,4',5-PeCB 123 65510-44-3
2',3,4,5,5'-PeCB 124 70424-70-3
2',3,4,5,6'-PeCB 125 74472-39-2
3,3',4,4',5-PeCB 126 57465-28-8
3,3',4,5,5'-PeCB 127 39635-33-1
2,2',3,3',4,4'-HxCB 128 38380-07-3
2,2',3,3',4,5-HxCB 129 55215-18-4
2,2',3,3',4,5'-HxCB 130 52663-66-8
2,2',3,3',4,6-HxCB 131 61798-70-7
2,2',3,3',4,6'-HxCB 132 38380-05-1
2,2',3,3',5,5'-HxCB 133 35694-04-3
2,2',3,3',5,6-HxCB 134 52704-70-8
2,2',3,3',5,6'-HxCB 135 52744-13-5
2,2',3,3',6,6'-HxCB 136 38411-22-2
2,2',3,4,4',5-HxCB 137 35694-06-5
2,2',3,4,4',5'-HxCB 138 35065-28-2
2,2',3,4,4',6-HxCB 139 56030-56-9
2,2',3,4,4',6'-HxCB 140 59291-64-4
2,2',3,4,5,5'-HxCB 141 52712-04-6
2,2',3,4,5,6-HxCB 142 41411-61-4
2,2',3,4,5,6'-HxCB 143 68194-15-0
2,2',3,4,5',6-HxCB 144 68194-14-9
2,2',3,4,6,6'-HxCB 145 74472-40-5
2,2',3,4',5,5'-HxCB 146 51908-16-8
2,2',3,4',5,6-HxCB 147 68194-13-8
2,2',3,4',5,6'-HxCB 148 74472-41-6
2,2',3,4',5',6-HxCB 149 38380-04-0
2,2',3,4',6,6'-HxCB 150 68194-08-1
2,2',3,5,5',6-HxCB 151 52663-63-5
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2,2',3,5,6,6'-HxCB 152 68194-09-2
2,2',4,4',5,5'-HxCB 153 35065-27-1
2,2',4,4',5',6-HxCB 154 60145-22-4
2,2',4,4',6,6'-HxCB 155 33979-03-2
2,3,3',4,4',5-HxCB 156 38380-08-4
2,3,3',4,4',5'-HxCB 157 69782-90-7
2,3,3',4,4',6-HxCB 158 74472-42-7
2,3,3',4,5,5'-HxCB 159 39635-35-3
2,3,3',4,5,6-HxCB 160 41411-62-5
2,3,3',4,5',6-HxCB 161 74472-43-8
2,3,3',4',5,5'-HxCB 162 39635-34-2
2,3,3',4',5,6-HxCB 163 74472-44-9
2,3,3',4',5',6-HxCB 164 74472-45-0
2,3,3',5,5',6-HxCB 165 74472-46-1
2,3,4,4',5,6-HxCB 166 41411-63-6
2,3',4,4',5,5'-HxCB 167 52663-72-6
2,3',4,4',5',6-HxCB 168 59291-65-5
3,3',4,4',5,5'-HxCB 169 32774-16-6
2,2',3,3',4,4',5-H CB 170 35065-30-6
2,2'3,3',4,4',6-HpCB 171 52663-71-5
2,2',3,3',4,5,5'-HpCB 172 52663-74-8
2,2',3,3',4,5,6-HpCB 173 68194-16-1
2,2',3,3',4,5,6'-HpCB 174 38411-25-5
2,2',3,3',4,5',6-HpCB 175 40186-70-7
2,2',3,3',4,6,6'-HpCB 176 52663-65-7
2,2',3,3',4',5,6-H CB 177 52663-70-4
2,2',3,3',5,5',6-HpCB 178 52663-67-9
2,2',3,3',5,6,6'-HpCB 179 52663-64-6
2,2',3,4,4',5,5'-H CB 180 35065-29-3
2,2',3,4,4',5,6-HpCB 181 74472-47-2
2,2',3,4,4',5,6'-HpCB 182 60145-23-5
2,2',3,4,4',5',6-HpCB 183 52663-69-1
2,2',3,4,4',6,6'-H CB 184 74472-48-3
2,2',3,4,5,5',6-HpCB 185 52712-05-7
2,2',3,4,5,6,6'-HpCB 186 74472-49-4
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SECTIONFIVE
Analytical Methods and Procedures
Table 5-1. PCB Congeners and Aroclors for Methods 1668 and 8082.
Method 1668
PCB Congener/Aroclor Congener Number CAS Number
2,2',3,4',5,5',6-HpCB 187 52663-68-0
2,2',3,4',5,6,6'-H CB 188 74487-85-7
2,3,3',4,4',5,5'-HpCB 189 39635-31-9
2,3,3',4,4',5,6-HpCB 190 41411-64-7
2,3,3',4,4',5',6-H CB 191 74472-50-7
2,3,3',4,5,5',6-HpCB 192 74472-51-8
2,3,3',4',5,5',6-HpCB 193 69782-91-8
2,2',3,3',4,4',5,5'-OcCB 194 35694-08-7
2,2',3,3',4,4',5,6-OcCB 195 52663-78-2
2,2',3,3',4,4',5,6'-OcCB 196 42740-50-1
2,2',3,3',4,4',6,6'-OcCB 197 33091-17-7
2,2',3,3',4,5,5',6-OcCB 198 68194-17-2
2,2',3,3',4,5,5',6'-OcCB 199 52663-75-9
2,2',3,3',4,5,6,6'-OcCB 200 52663-73-7
2,2',3,3',4,5',6,6'-OcCB 201 40186-71-8
2,2',3,3',5,5',6,6'-OcCB 202 2136-99-4
2,2',3,4,4',5,5',6-OcCB 203 52663-76-0
2,2',3,4,4',5,6,6'-OcCB 204 74472-52-9
2,3,3',4,4',5,5',6-OcCB 205 74472-53-0
2,2',3,3',4,4',5,5',6-NoCB 206 40186-72-9
2,2',3,3',4,4',5,6,6'-NoCB 207 52663-79-3
2,2',3,3',4,5,5',6,6'-NoCB 208 52663-77-1
DeCB 209 2051-24-3
Method 8082
Aroclor 1016 NA 12674-11-2
Aroclor 1221 NA 11104-28-2
Aroclor 1232 NA 11141-16-5
Aroclor 1242 NA 53469-21-9
Aroclor 1248 NA 12672-29-6
Aroclor 1254 NA 11097-69-1
Aroclor 1260 NA 11096-82-5
Abbreviations
DeCB = decachlorobiphenyl NoCB = nonachlorobiphenyl
DiCB = dichlorobiphenyl OcCB = octachlorobiphenyl
HpCB = heptachlorobiphenyl PeCB = pentachlorobiphenyl
HxCB = hexachlorobiphenyl TeCB = tetrachlorobiphenyl
MoCB = monochlorobiphenyl TrCB = trichlorobiphenyl
NA = Not Applicable
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SECTIONFIVE
Analytical Methods and Procedures
Dioxin congeners will be analyzed using Method 1613. The following table presents the
congeners which will be reported by the analytical laboratory (Table 5-2).
Table 5-2 Analyte for Method 1613A
CDDs/CDFs CAS Number
2,3,7,8-TCDD 1746-01-6
Total TCDD 41903-57-5
2,3,7,8-TCDF 51207-31-9
Total-TCDF 55722-27-5
1,2,3,7,8-PeCDD 40321-76-4
Total-PeCDD 36088-22-9
1,2,3,7,8-PeCDF 57117-41-6
2,3,4,7,8-PeCDF 57117-31-4
Total-PeCDF 30402-15-4
1,2,3,4,7,8-HxCDD 39227-28-6
1,2,3,6,7,8-HxCDD 57653-85-7
1,2,3,7,8,9-HxCDD 19408-74-3
Total-HxCDD 34465-46-8
1,2,3,4,7,8-HxCDF 70648-26-9
1,2,3,6,7,8-HxCDF 57117-44-9
1,2,3,7,8,9-HxCDF 72918-21-9
2,3,4,6,7,8-HxCDF 60851-34-5
Total-HxCDF 55684-94-1
1,2,3,4,6,7,8-HpCDD 35822-46-9
Total-HpCDD 37871-00-4
1,2,3,4,6,7,8-H CDF 67562-39-4
112,3,4,7,8,9-HpCDF 55673-89-7
Total-HpCDF 38998-75-3
OCDD 3268-87-9
OCDF 39001-02-0
Abbreviations
CDD = Chlorinated dibenzo-p-dioxins
CDF = Chlorinated dibenzofurans
HxCDD = Hexachlorodibenzo-p-dioxin
HpCDD = Heptachlorodibenzo-p-dioxin
HpCDF = Heptachlorodibenzofuran
HxCDF = Hexachlorodibenzofuran
OCDD = Octachlorodibenzo-p-dioxin
OCDF = Octachlorodibenzofuran
PeCDD = Pentachlorodibenzo-p-dioxin
PeCDF = Pentachlorodibenzofuran
TCDD = Tetrachlorodibenzo-p-dioxin
TCDF = Tetrachlorodibenzofuran
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SECTIONFIVE Analytical Methods and Procedures
Methods 1668 and 1613 have their own specific QC criteria hard written into the method. The
laboratory will adhere to the specific requirements of those methods. Method 8082 in part uses
control limits generated by laboratory for various QC parameters. A complete description for
these methods is included in Pace Analytical, Inc SOPS (Appendix A). Acceptance criteria for
the accuracy of spiked analyte and surrogate recoveries (if applicable), and the acceptance
criteria for the precision of matrix, field, and laboratory duplicate recoveries are also provided in
Appendix A.
5.3 LABORATORY DATA QUALIFIERS
The laboratory shall in general qualify data using the CLP Statement of Work Qualifiers. They
may, at their option use additional lab qualifiers, or use different lab qualifiers if that is their
practice, provided that a full key to the qualifiers is provided in the data package. At minimum,
the lab shall qualify the data for the occurrences listed in Table 5-5 below, for each method
where applicable.
Table 5-3. Laboratory Data Qualifiers.
Qualifier Description

U The analyte was analyzed for, but not detected. The associated numerical value is at or
below the MDL.
J The analyte was presumptively identified above the MDL but the associated numerical
value is below the RL.
R Data was rejected by the lab due to an uncorrectable major QC problem
B The analyte was found in an associated blank, as well as in the sample.
M A matrix effect was present. (Failure of MS/MSD recovery or RPD)
N This flag indicates presumptive evidence of a compound detected on only one column.
Not required if Aroclor pattern is clearly identifiable.
P This flag is used for a pesticide/Aroclor target analyte when there is greater than 25%
difference for detected concentrations between two GC columns.
E This flag identifies compounds whose concentrations exceed the upper level of the
calibration range of the instrument for that specific analysis.
D This flag is used for all compounds quantified from an analysis at a secondary dilution
factor. This result replaces corresponding "E" qualified result, if above the dilution
adjusted reporting limit, and all QC parameters are acceptable.
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SECTIONSIX Data Reduction, Review, Verification,
Reporting, Validation and Recordkeeping
The data reduction, review, reporting, and validation procedures described in this section will
ensure (1) complete documentation is maintained, (2) transcription and data reduction errors are
minimized, (3) the data are reviewed and documented, and (4) the reported results are qualified,
if necessary. Laboratory data reduction and verification procedures will ensure the overall
objectives of analysis and reporting meet method and project specifications.
6.1 DATA REVIEW, VALIDATION, AND REPORTING REQUIREMENTS FOR
DEFINITIVE DATA
MDLs and sample results will be reported to one decimal place more than the corresponding RL,
unless the appropriate number of significant figures for the measurement dictates otherwise. Fish
tissue sample analyses will have results reported on a wet weight basis. RLs for minority
constituents in highly contaminated samples may be adjusted for dilutions.
In each laboratory analytical section, the analyst performing the tests will review 100% of the
definitive data. After the analyst's review is complete, 100% of the data will be reviewed
independently by a senior analyst or by the supervisor of the respective analytical section using
the same criteria.
The definitive data methods are identified in Section 5.2. The calibration, QC requirements,
corrective action requirements, and flagging criteria required for definitive data are shown in the
tables in Section 5.2 and summarized in Tables 5-2 and 5-3. The flagging criteria will be applied
when acceptance criteria are not met and corrective action was not successful or corrective action
was not performed.
Laboratory data qualifiers will be added or, if applied by a software package, reviewed by the
laboratory supervisor of the respective analytical section, after the first and second level of
laboratory data reviews have been performed. Analytical batch comments will be added to the
first page of the definitive data report packages to explain any nonconformance or other issues.
Data validation will be performed by a URS Senior Chemist. The lab must furnish a full Level
IV data package in "Contract Laboratory Program (CLP)-like" format, which includes all
relevant CLP raw data and summaries, and a case narrative describing any QC variance
encountered during the analyses. This format should be in both hard copy and Adobe acrobat
(pdf) format. In addition, the lab must provide electronic data deliverables (EDDs) in summary
format that is sufficient to contain both lab and field IDs for all samples, the results with units
designated, all MDL and RL values, sampling and analytical dates and times, and any dilution or
analytical batch information required to trace the results to the raw analytical data. Table 6-1 is a
list of the validation qualifiers that will be applied to the data. This list is consistent with the
National Functional Guidelines for Organic Data Review (USEPA 1999).
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SECTIONSIX
Data Reduction, Review, Verification,
Reporting, Validation and Recordkeeping
Table 6-1. Interpretive Data Qualifiers
Qualifier Description
U The analyte should be considered not detected at the reported value for the reasons discussed in
the validation report. This is distinct from the laboratory U or BQL qualifiers, which means
that the analyte was simply not detected.
J For the GCMS data the identification of the analyte is acceptable, but quality assurance criteria
indicate that the quantitative values may be outside the normal expected range of precision,
i.e., the quantitative value is considered estimated. For non-MS data, both the presence and
quantitation of the compound is uncertain.
N There is presumptive evidence that the analyte is present, but it has not been confirmed. The
analyte is "tentatively identified". There is an indication that the reported analyte is present,
however, all quality control requirements necessary for confirmation were not met. This is
applicable to pesticide and PCB data.
R Data are considered to be rejected and shall not be used. This flag denotes the failure of
quality control criteria such that it cannot be determined if the analyte is present or absent from
the sample. Resampling and analysis are necessary to confirm or deny the presence of the
analyte.
C This flag is most often used in conjunction with pesticides/PCB data. The analyte is
determined to be present and the presence has been confirmed by GUMS.
UJ This is a combination of the U and J flags. The analyte is not considered to be present. The
reported value is considered to be an estimated limit of detection.
JN A combination of the J and N flags. The analyte is tentatively identified and the value
preceding the JN is estimated.
DUP For this report, this flag designates a quantifiable field duplicate result that did not meet QAPP
RPD criteria.
In general, data will be validated using the National Functional Guidelines for Organic Data
Review (USEPA, 1999) with changes and allowances made to conform to SW-846 methodology
(USEPA 1996). Tables 6-2 and 6-3 contain examples of validation actions and qualifiers based
on the most common QC variances.
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SECTIONSIX
Data Reduction, Review, Verification,
Reporting, Validation and Recordkeeping
Table 6-2 General Validation Flagging Conventions
QC Requirement Criteria Fla Fla Applied To
Holding Time Time exceeded for J for detected results, R All analytes in the sample
extraction or analysis for non-detected results
o%R > UCL J for the positive results The specific analyte in all
LCS oR < LCL
/ J for the positive results, samples in the associated
UJ for the non-detects
analytical group
%R<10% R for all
UJ if <5X blk The specific analyte in all
Method Blank Analyte detected >_ J if <10X, except for samples in the associated
MDL known lab contaminants analytical group with
. results above the MDL
The specific analyte in all
Analyte detected >_ samples with the same
Equipment Blank MDL Judgement sampling date as the
equipment blank with
results above the MDL
Results >RL AND DUP for the positive The specific analyte in all
Field duplicates RPD outside CL results samples collected on the
R for the nondetects same sampling date
MS or MSD %R >UCL J, UJ, depending on
The specific analyte in all
OR violation, detection in samples collected from the
MS/MSD MS or MSD %R <LCL sample, R if minimum same site as the parent
OR criteria (>10% recovery) sample
MS/MSD RPD >CL not met
Sample Preservation/ Preservation/Collection R, J, or UJ for all results, All analytes in the sample
Collection requirements not met based on judgment
<2°C or >6°C or as J for the positive results
Sample Storage required UJ or R for the All analytes in the sample
nondetects
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SECTIONSIX Data Reduction, Review, Verification,
Reporting, Validation and Recordkeeping
Table 6-3. Validation Flagging Conventions for Organic Methods.
QC Requirement Criteria Fla Fla Applied To
Initial Five Point Response or R The specific analyte in all samples associated
Calibration (GC and Linearity criteria with the initial calibration
HPLC methods) not met
Initial Five Point SPCC or CCC R All analytes in all samples associated with the
Calibration(GC/MS criteria not met initial calibration
methods) Linearity criterion R The specific analyte in all samples associated
not met with the initial calibration
Initial Daily CL exceeded J, UJ, or R The specific analyte in all samples associated
Calibration (Judgment) with the initial calibration verification
Verification (GC,
GCMS, and HPLC
methods)
Calibration CL exceeded with Jfor the The specific analyte in all samples associated
Verification (GC and positive bias positive results with the calibration verification
HPLC methods) CL exceeded with Jfor the The specific analyte in all samples associated
negative bias positive results with the calibration verification
UJ or R for the
nondetects
Retention Time Retention time of R The specific analyte in the sample
analyte outside of
established
retention time
window
Surrogates More than one J for the positive All analytes in the sample associated with the
surrogate %R results surrogate, unless the extract was diluted by a
>UCL factor of four or greater due to high analyte
OR J for the positive concentration or interference
More than one results
surrogate %R UJ for the non-
<LCL detects
OR R for all results
Any surrogate
recovery <10%
Second Not performed N, except All affected analytes _RL
Column/Second Method 8082,
Detector Confirmation distinct Aroclor
(GC and HPLC Agreement between pattern
methods) results not within All affected analytes
±40% JN
All affected analytes
ND on second UJ
column
URS will review and validate the entire definitive data report package, and with the field records,
apply the final data qualifiers for the definitive data. A validation report will be provided as an
Appendix to the final report. The validation report will contain complete explanations for the
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SECTIONSIX Data Reduction, Review, Verification,
Reporting, Validation and Recordkeeping
issuance of any validation qualifiers, and also contain complete tables documenting all validation
qualifiers issued, along with a summary of the reason for each.
URS, as a part of the validation report, will catalog and assess any deviations from the QAPP,
will determine finally whether the DQOs have been met, and calculate data completeness for the
proj ect.
6.2 QUALITY ASSURANCE REPORTS
The laboratory QA staff will issue QA reports to laboratory management, laboratory supervisors,
and task leaders. These reports will describe the results of QC measurements, performance
audits, systems audits, and confirmation sample comparisons performed for each sampling and
analysis task. Quality problems associated with performance of methods, completeness of data,
comparability of data including field and confirmatory data, and data storage will be documented
with the corrective actions that have been taken.
6.3 HARD COPY DATA REPORTS AND ARCHIVING
Complete laboratory electronic data files (pdf format) will be included as an Appendix to the
final project report deliverable. Hardcopy and electronic data will be archived in project files
and on electronic archive tapes for the duration of the project or a minimum of 5 years,
whichever is longer.
6.4 PROJECT DATA FLOW AND TRANSFER
Data flow from the laboratory and field to the project staff and data users will be sufficiently
documented to ensure the data are properly tracked, reviewed, and validated for use.
6.5 RECORDKEEPING
The laboratory will maintain electronic and hardcopy records sufficient to recreate each
analytical event conducted. The minimum records the laboratory will retain include (1) COC
forms; (2) initial and continuing calibration records, including standards preparation traceable to
the original material and lot number; (3) instrument tuning records (as applicable); (4) method
blank results; (5) IS results; (6) surrogate spiking records and results (as applicable); (7) spike
and spike duplicate records and results; (8) laboratory records; (9) raw data, including instrument
printouts, bench work sheets, and/or chromatograms with compound identification and
quantitation reports; (10) corrective action reports; (11) other method and project required QC
samples and results; and (12) laboratory-specific written SOPS for each analytical method and
QA/QC function in place at the time of analysis of project samples.
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SECTIONSEVEN
Project Audits and Training
7.1 PROJECT AUDITS
Laboratory or field audits may be conducted during the course of this project. Audits, external or
internal, that reveal noncompliance or deviations with regard to field activities or laboratory
methods and procedures will be addressed in writing by URS with corrective actions and a time
frame for implementation of the corrective actions.
7.2 TRAINING
Training will be provided to all project personnel in compliance with the Health and Safety Plan.
Documentation of this training will be maintained in the project file.
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SECTIONEIGHT
Corrective Actions
Corrective actions, if necessary, will be completed at once if acceptance criteria are not met. If a
corrective action was not successful or corrective action was not performed, the appropriate
flagging criteria will be applied.
Problems requiring corrective action in the laboratory will be documented by the use of a
corrective action report. The QA coordinator or any other laboratory member will initiate the
corrective action request in the event QC results exceed acceptability limits or upon
identification of some other laboratory problem. Corrective actions will include reanalysis of the
sample or samples affected, resampling and analysis, or a change in procedures, depending upon
the severity of the problem.
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SECTIONNINE
References
USEPA. (1999). SW-846 Third Edition, Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods, Update IIIB.. Solid Waste. Washington D. C.: USEPA.
USEPA. (1999). USEPA Contract Laboratory Program National Functional Guidelines for
Organic Data Review. EPA-540/R-99-008 (PB99-963506).
USEPA. 1996. SW-846 Third Edition, Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods, Update IIIB. Available online at
http://www.epa.gov/epaoswer/hazwaste/test/up3b.htm.
USEPA. 1999. USEPA Contract Laboratory Program National Functional Guidelines for
Organic Data Review. EPA-540/R-99-008 (PB99-963506). October 1999.
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Appendix A
Pace SOP for PCB Analysis and Detection Limits
ii z,
ace Analytical
i
QUALITY ASSURANCE MANUAL
Quality Assurance/Quality Control
Policies and Procedures
Revision 11.0
Pace Analytical Services - Minnesota
1700 Elm Street SE, Suite 200
Minneapolis, MN 55414
612-607-1700
CO R 1-0 RAT F., APPROV A].

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Prc- s icicikl, C F0
1700 f:Lrti StTCEt SF., Soli . 200
Minneapolis, MN 55414
(61') 6017-1700

Brad A- Mectdow:
DjIV(`.J(Mr (.16' QillgilY, ?.if?.Jy, ?Itt({ I C'.Vhr ok).gy
1700 Elrii Sir-eel .SE, Suxe 200
Mimicapolis, NIN 55414
(f612) 60-J-1700
Bale

C 2002 - 2007 Pace Analytical Services, Inc. This Quality Assurance Manual may not be reproduced, in part or in full, without written consent
of Pace Analytical Services, Inc. Whether distributed internally or as a "courtesy copy" to customers or regulatory agencies, this document is
considered confidential and proprietary information.
Any printed documents in use within a Pace Analytical Services, Inc. laboratory have been reviewed and approved by the persons listed on the
cover page. They can only be deemed official if proper signatures are present.
This is COPY# 17 distributed on 16NOV2007_ by MRO and is CONTROLLED or X UNCONTROLLED.
Quality Assurance Manual
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PACE ANALYTICAL SERVICES - MINNESOTA
LOCAL APPROVAL
This €idxR.esrac Ott laa 1. eat a1+p'm t1 t1>. Quality =sttrama lWla ru a1, el i'ee ire a i
indheated lxy the fallowing signatuir is
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Laboratory ocncral A'la?ftger Date
612-(>07-6354
Laboi ry 1?cgiosial Quality Manager Date
012-619-4104
Laboratory t: uality Manavf-r Tate
612-0117-6352
I,ahoratory ° zelinic aI DiivcIiir - Chctni.try Date
612-607-6506
L
Laboratory ' .chnic:al Director - Dioxin Date.
612-607-03387
- "44
Laboratory T?,,cbnicid Dii-emor - Air D tto
012-607-6386
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Table of Contents
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1.0 INTRODUCTION AND ORGANIZATIONAL STRUCTURE .................................................................. 5
1.1 INTRODUCTION TO PASI .................................................................................................. .......................... 5
1.2 STATEMENT OF PURPOSE ................................................................................................. .......................... 5
1.3 QUALITY POLICY STATEMENT AND GOALS OF THE QUALITY SYSTEM ......................... .......................... 5
1.4 PACE ANALYTICAL SERVICES CORE VALUES ................................................................. .......................... 5
1.5 CODE OF ETHICS .............................................................................................................. .......................... 6
1.6 STANDARDS OF CONDUCT ................................................................................................ .......................... 6
1.7 LABORATORY ORGANIZATION ........................................................................................ .......................... 7
1.8 LABORATORY JOB DESCRIPTIONS ................................................................................... .......................... 8
1.9 TRAINING AND ORIENTATION .......................................................................................... ........................ 11
1.10 LABORATORY SAFETY ....................................................................................................... ........................ 12
1.11 SECURITY AND CONFIDENTIALITY .................................................................................... ........................ 13
2.0 SAMPLE CUSTODY ........................................................................................................................................14
2.1 SAMPLING SUPPORT .................................................................................. ............................................... 14
2.2 PROJECT INITIATION ................................................................................. ............................................... 14
2.3 CHAIN-OF-CUSTODY ................................................................................. ...............................................14
2.4 SAMPLE ACCEPTANCE POLICY ................................................................. ............................................... 15
2.5 SAMPLE LOG-IN ......................................................................................... ............................................... 16
2.6 SAMPLE STORAGE ..................................................................................... ............................................... 17
2.7 SAMPLE PROTECTION ............................................................................... ............................................... 18
2.8 SUBCONTRACTING ANALYTICAL SERVICES ............................................... ............................................... 18
2.9 SAMPLE RETENTION AND DISPOSAL .......................................................... ............................................... 19
3.0 ANALYTICAL CAPABILITIES ...................................................................................................................... 20
3.1 ANALYTICAL METHOD SOURCES .............................................................................................................. 20
3.2 ANALYTICAL METHOD DOCUMENTATION .............................................................................................. 20
3.3 ANALYTICAL METHOD VALIDATION ........................................................................................................ 20
3.4 DEMONSTRATION OF CAPABILITY (DOC) ................................................................................................. 20
3.5 REGULATORY AND METHOD COMPLIANCE .............................................................................................. 21
4.0 QUALITY CONTROL PROCEDURES ......................................................................................................... 22
4.1 DATA INTEGRITY SYSTEM ........................................................................................................................ 22
4.2 METHOD BLANK ....................................................................................................................................... 22
4.3 LABORATORY CONTROL SAMPLE ............................................................................................................ 23
4.4 MATRIX SPIKE/MATRIX SPIKE DUPLICATE (MS/MSD) ......................................................................... 24
4.5 SURROGATES ............................................................................................................................................ 24
4.6 SAMPLE DUPLICATE ................................................................................................................................. 25
4.7 INTERNAL STANDARDS ............................................................................................................................. 25
4.8 FIELD BLANKS .......................................................................................................................................... 25
4.9 TRIP BLANKS ............................................................................................................................................ 25
4.10 LIMIT OF DETECTION (LOD) ................................................................................................................... 25
4.11 LIMIT OF QUANTITATION (LOQ) ............................................................................................................ 26
4.12 ESTIMATE OF UNCERTAINTY ................................................................................................................... 26
4.13 PROFICIENCY TESTING (PT) STUDIES ..................................................................................................... 26
4.14 ROUNDING AND SIGNIFICANT FIGURES ................................................................................................... 27
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5.0 DOCUMENT MANAGEMENT AND CHANGE CONTROL ............................................................... 28
5.1 DOCUMENT MANAGEMENT ...................................................................................................................... 28
5.2 DOCUMENT CHANGE CONTROL ............................................................................................................... 29
6.0 EQUIPMENT AND MEASUREMENT TRACEABILITY .......................................................................... 30
6.1 STANDARDS AND TRACEABILITY ............................................................................................................. 30
6.2 GENERAL ANALYTICAL INSTRUMENT CALIBRATION PROCEDURES ...................................................... 30
6.3 SUPPORT EQUIPMENT CALIBRATION PROCEDURES .................................................................................. 33
6.4 INSTRUMENT/ EQUIPMENT MAINTENANCE ............................................................................................... 34
7.0 CONTROL OF DATA ....................................................................................................................................... 36
7.1 ANALYTICAL RESULTS PROCESSING ......................................................................................................... 36
7.2 DATA VERIFICATION ................................................................................................................................. 36
7.3 DATA REPORTING ..................................................................................................................................... 37
7.4 DATA SECURITY ........................................................................................................................................ 38
7.5 DATA ARCHIVING ...................................................................................................................................... 38
7.6 DATA DISPOSAL ........................................................................................................................................ 38
8.0 QUALITY SYSTEM AUDITS AND REVIEWS ........................................................................................... 39
8.1 INTERNAL AUDITS .................................................................................................................................... 39
8.2 EXTERNAL AUDITS .................................................................................................................................... 40
8.3 QUARTERLY QUALITY REPORTS .............................................................................................................. 41
8.4 ANNUAL MANAGERIAL REVIEW .............................................................................................................. 41
9.0 CORRECTIVE ACTION ................................................................................................................................. 42
9.1 CORRECTIVE ACTION DOCUMENTATION .................................................................................................. 42
9.2 CORRECTIVE ACTION COMPLETION ......................................................................................................... 42
10.0 GLOSSARY ................................................................................................................................................. 45
11.0 REFERENCES ............................................................................................................................................... 51
12.0 REVISIONS ................................................................................................................................................... 52
ATTACHMENT I ................................................................................................................................................... 55
ATTACHMENT IIA ............................................................................................................................................... 57
ATTACHMENT IIB ............................................................................................................................................... 58
ATTACHMENT III ................................................................................................................................................ 59
ATTACHMENT IV ................................................................................................................................................ 62
ATTACHMENT V .................................................................................................................................................. 63
ATTACHMENT VI ................................................................................................................................................ 67
ATTACHMENT VII ............................................................................................................................................... 70
ATTACHMENT VIII ............................................................................................................................................. 71
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1.0 INTRODUCTION AND ORGANIZATIONAL STRUCTURE
"Working together to protect our environment and improve our health"
Pace Analytical Services Inc. - Mission Statement
1.1 Introduction to PASI
Pace Analytical Services, Inc. (PASI) is a privately held, full-service analytical testing firm operating a
nationwide system of laboratories. PASI offers extensive services beyond standard analytical testing,
including: bioassay for aquatic toxicity, air toxics, industrial hygiene testing, explosives, high resolution mass
spectroscopy (including dioxins, furans and coplanar PCB's), radiochemical analyses, product testing,
pharmaceutical testing, field services and mobile laboratory capabilities. PASI has implemented a consistent
Quality System in each of its laboratories and service centers. In addition, the company utilizes an advanced
data management system that is highly efficient and allows for flexible data reporting. Together, these systems
ensure data reliability and superior on-time performance. This document defines the Quality System and
QA/QC protocols.
Our goal is to combine our expertise in laboratory operations with customized solutions to meet the specific
needs of our customers.
1.2 Statement of Purpose
To meet the business needs of our customers for high quality, cost-effective analytical measurements and
services.
1.3 Quality Policy Statement and Goals of the Quality System
The PASI management is committed to maintaining the highest possible standard of service for our
customers by following a documented quality system. The overall objective of this quality system is to
provide reliable data through adherence to rigorous quality assurance policies and quality control
procedures as documented in this Quality Assurance Manual.
All personnel within the PASI network are required to be familiar with all facets of the quality system and
implement these policies and procedures in their daily work. This daily focus on quality is applied with
initial project planning, continued through all field and laboratory activities, and is ultimately included in
the final report generation.
PASI management demonstrates its commitment to quality by providing the resources, including facilities,
equipment and personnel to ensure the adherence to these documented policies and procedures and to
promote the continuous improvement of the quality system. All PASI personnel comply with all current
applicable state, federal, and industry standards (such as the NELAC and ISO 17025 standards).
1.4 Pace Analytical Services Core Values
• INTEGRITY
• VALUE EMPLOYEES
• KNOW OUR CUSTOMERS
• HONOR COMMITMENTS
• FLEXIBLE RESPONSE TO DEMAND
• PURSUE OPPORTUNITIES
• CONTINUOUSLY IMPROVE
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1.5 Code of Ethics
PASI's fundamental ethical principles are as follows:
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Each PASI employee is responsible for the propriety and consequences of his or her actions.
Each PASI employee must conduct all aspects of Company business in an ethical and strictly legal
manner, and must obey the laws of the United States and of all localities, states and nations where
PASI does business or seeks to do business.
Each PASI employee must reflect the highest standards of honesty, integrity and fairness on behalf of
the Company with customers, suppliers, the public, and one another.
Strict adherence by each PASI employee to this Code of Ethics and to the Standards of Conduct is
essential to the continued vitality of PASI.
Failure to comply with the Code of Ethics and Standards of Conduct will result in disciplinary action up to
and including termination and referral for civil or criminal prosecution where appropriate. An employee
will be notified of an infraction and given an opportunity to explain, as prescribed under current
disciplinary procedures.
1.6 Standards of Conduct
1.6.1 Data Integrity
The accuracy and integrity of the analytical results produced at PASI are the cornerstones of the
company. Lack of data integrity is an assault on our most basic values and puts PASI and its
employees at grave financial and legal risk. Therefore, employees are to accurately prepare and
maintain all technical records, scientific notebooks, calculations and databases. Employees are
prohibited from making false entries or misrepresentations of data (e.g., dates, calculations, results or
conclusions).
Managerial staff must make every effort to ensure that personnel are free from any undue pressures
that may affect the quality or integrity of their work; including commercial, financial, over-
scheduling and working condition pressures.
1.6.2 Confidentiality
PASI employees must not (directly or indirectly) use or disclose confidential or proprietary
information except when in connection with their duties at PASL This is effective over the course of
employment and for a period of two years thereafter.
Confidential or proprietary information, belonging to either PASI and/or its customers, includes but
is not limited to test results, trade secrets, research and development matters, procedures, methods,
processes and standards, company-specific techniques and equipment, marketing and client
information, inventions, materials composition, etc.
1.6.3 Conflict of Interest
PASI employees must avoid situations that might involve a conflict of interest or appear questionable
to others. The employee must be careful in two general areas:
• Participation in activities that conflict or appear to conflict with PASI responsibilities.
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Offering or accepting anything that might influence the recipient or cause another person to
believe that the recipient may be influenced. This includes bribes, kickbacks or illegal
payments.
Employees are not to engage in outside business or economic activity relating to a sale or purchase
by the Company. Other questionable activities include service on the Board of Directors of a
competing or supplier company, significant ownership in a competing or supplier company,
employment for a competing or supplier company or participation in any outside business during the
employee's work hours.
1.6.4 Compliance
All employees are required to read, understand and comply with the various components of the
standards listed in this document As confirmation that they understand this responsibility, each
employee is required to sign an acknowledgment form annually that becomes part of the employee's
permanent record. Employees will be held accountable for complying with the Quality Systems as
summarized in the Quality Assurance Manual.
1.7 Laboratory Organization
The PASI Corporate Office centralizes company-wide accounting, business development, financial
management, human resources development, information systems, marketing, quality, safety, and training
activities. PASI's Director of Quality, Safety & Technology is responsible for assisting the development,
implementation and monitoring of quality programs for the company. See Attachment IIB for the
Corporate Organizational structure.
Each laboratory within the system operates with local management, but all share common systems and
receive support from the Corporate Office.
A General Manager (GM) supervises each regional laboratory. Some operations may have an Assistant
General Manager (AGM) in situations where the General Manager is responsible for multiple laboratory
facilities and is not necessarily in the facility on a regular basis. Quality Managers (QM) at each lab report
directly to their General Manager (or Assistant General Manager) but receive guidance and direction from the
Director of Quality, Safety & Technology.
The General Manager bears the responsibility for the laboratory operations and serves as the final, local
authority in all matters. In the absence of the General Manager (and an Assistant General Manager), the
Quality Manager serves as the next in command. He or she assumes the responsibilities of the GM until the
GM is available to resume the duties of their position. In the absence of the GM and QM, management
responsibility of the laboratory is passed to the Technical Director - provided such a position is identified -
and then to most senior department manager until the return of the GM or QM. The most senior department
manager in charge may include the Client Services Manager or the Administrative Business Manager at the
discretion of the General Manager.
A Technical Director who is absent for a period of time exceeding 15 consecutive calendar days shall
designate another full-time staff member meeting the qualifications of the technical director to temporarily
perform this function. The laboratory General Manager or Quality Manager has the authority to make this
designation in the event the existing Technical Director is unable to do so. If this absence exceeds 65
consecutive calendar days, the primary accrediting authority shall be notified in writing.
The Quality Manager has the responsibility and authority to ensure the Quality System is implemented and
followed at all times. In circumstances where a laboratory is not meeting the established level of quality or
following the policies set for in this Quality Assurance Manual, the Quality Manager has the authority to halt
laboratory operations should he or she deem such an action necessary. The QM will immediately
communicate the halting of operations to the GM and keep him or her posted on the progress of corrective
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actions. In the event the GM and QM are not in agreement as to the need for the suspension, the Chief
Operating Officer and Director of Quality, Safety and Technology will be called in to mediate the situation.
Under the direction of the General Manager, the technical staff of the laboratory is generally organized into the
following functional groups:
• Organic Sample Preparation
• Wet Chemistry Analysis
• Metals Analysis
• Volatiles Analysis
• Semi-volatiles Analysis
• Radiochemical Analysis
• Product Testing
• Equipment Maintenance
• Microbiology
Appropriate support groups are present in each laboratory. The actual organizational structure for PASI -
Minnesota is listed in Attachment IIA. In the event of a change in General Manager, Quality Manager or
Technical Director(s), the laboratory will notify its accrediting authorities and revise the organizational chart
in the Quality Assurance Manual (QAM) within 30 days. For changes in Department Managers or
Supervisors or other laboratory personnel, no notifications will be sent to the laboratory's accrediting
agencies; changes to the organizational chart will be updated during or prior to the annual review process.
Changes or additions in these key personnel will also be noted by the additional signatures on the QAM Local
Approval page. In any case, the QAM will remain in effect until the neat scheduled revision.
1.8 Laboratory Job Descriptions
1.8.1 General Manager
Oversees all functions of the operations.
Authorizes personnel development including staffing, recruiting, training, workload
scheduling, employee retention and motivation.
Prepares budgets and staffing plans.
Monitors the Quality Systems of the laboratory and advises the Quality Manager
accordingly.
Ensures compliance with all applicable state, federal and industry standards.
1.8.2 Quality Manager
1. Oversees the laboratory Quality Systems while functioning independently from laboratory
operations. Reports directly to the General Manager or Regional Quality Manager.
2. Monitors Quality Assurance policies and Quality Control procedures to ensure that the
laboratory achieves established standards of quality.
3. Maintains records of quality control data and evaluates data quality.
4. Conducts periodic internal audits and coordinates external audits performed by regulatory
agencies or client representatives.
5. Reviews and maintains records of proficiency testing results.
6. Maintains the document control system
7. Assists in development and implementation of appropriate training programs.
8. Provides technical support to laboratory operations regarding methodology and project
QA/QC requirements.
9. Maintains certifications from federal and state programs.
10. Ensures compliance with all applicable state, federal and industry standards.
11. Maintains the laboratory training records.
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1.8.3 Technical Director
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1. Monitors the standards of performance in quality assurance and quality control data
2. Monitors the validity of analyses performed and data generated.
3. Reviews tenders, contracts and QAPPs to ensure the laboratory can meet the data quality
objectives for any given project
4. Serves as the general manager of the laboratory in the absence of the GM, AGM and QM.
5. Provides technical guidance in the review, development and validation of new
methodologies.
1.8.4 Administrative Business Manager
1. Responsible for financial and administrative management for the entire facility.
2. Provides input relative to tactical and strategic planning activities.
3. Organizes financial information so that the facility is run as a fiscally responsible business.
4. Works with staff to confirm that appropriate processes are put in place to track revenues and
expenses.
5. Provide ongoing financial information to the General Manager and the management team so
they can better manage their business.
6. Utilizes historical information and trends to accurately forecast future financial positions.
7. Works with management to ensure that key measurements (mileposts) are put in place to be
utilized for tread analysis-this will include personnel and supply expenses, and key revenue
and expense ratios.
8. Works with General Manager to develop accurate budget and track on an ongoing basis.
9. Works with entire management team to submit complete and justified capital budget requests
and to balance requests across departments.
10. Works with project management team and administrative support staff to ensure timely and
accurate invoicing.
1.8.5 Client Services Manager
1. Oversees all the day to day activities of the Client Services Department which includes
Project Management and, possibly, Sample Control.
2. Responsible for staffing and all personnel management related issues for Client Services.
3. Serves as the primary senior consultant to clients on all project related issues such as set up,
initiation, execution and closure.
4. Performs or is capable of performing all duties listed for that of Project Manager.
1.8.6 Project Manager
1. Coordinates daily activities including taking orders, reporting data and analytical results.
2. Serves as the primary technical and administrative liaison between customers and PASI.
3. Communicates with operations staff to update and set project priorities.
4. Provides results to customers in the requested format (verbal, hardcopy, electronic, etc.).
5. Works with customers, laboratory staff, and other appropriate PASI staff to develop project
statements of work or resolve problems of data quality.
3. Responsible for solicitation of work requests, assisting with proposal preparation and project
initiation with customers and maintain client records.
4. Mediation of project schedules and scope of work through communication with internal
resources and management.
5. Responsible for preparing routine and non-routine quotations, reports and technical papers.
6. Interfaces between customers and management personnel to achieve client satisfaction.
7. Manages large-scale complex projects.
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Supervises less experienced project managers and provide guidance on management of
complex projects.
Arranges bottle orders and shipment of sample kits to customers.
Verifies login information relative to project requirements and field sample Chains-of-
Custody.
1.8.7 Project Coordinator
Responsible for preparation of project specifications and provides technical/project support.
Coordinates project needs with other department sections and assists with proposal
preparation.
Prepares routine proposals and invoicing.
Responsible for scanning, copying, assembling and binding final reports.
Other duties include filing, maintaining forms, process outgoing mail, maintaining training
database and data entry.
1.8.8 Department Manager/Supervisor
1. Oversees the day-to-day production and quality activities of their assign department.
2. Ensures that quality assurance and quality control criteria of analytical methods and projects
are satisfied.
3. Assesses data quality and takes corrective action when necessary.
4. Approves and releases technical and data management reports.
5. Ensures compliance with all applicable state, federal and industry standards.
1.8.9 Group Supervisor/Leader
Trains analysts in laboratory operations and analytical procedures.
Organizes and schedules analyses with consideration for sample holding times.
Implements data verification procedures by assigning data verification duties to appropriate
personnel.
Evaluates instrument performance and supervises instrument calibration and preventive
maintenance programs.
Reports non-compliance situations to laboratory management including the Quality
Manager.
1.8.10 Laboratory Analyst
Performs detailed preparation and analysis of samples according to published methods and
laboratory procedures.
Processes and evaluates raw data obtained from preparation and analysis steps.
Generates final results from raw data, performing primary review against method criteria.
Monitors quality control data associated with analysis and preparation. This includes
examination of raw data such as chromatograms as well as an inspection of reduced data,
calibration curves, and laboratory notebooks.
Reports data in LIMS, authorizing for release pending secondary approval.
Conducts routine and non-routine maintenance of equipment as required.
Performs or is capable of performing all duties associated with that of Laboratory
Technician.
1.8.11 Laboratory Technician
1. Prepares standards and reagents according to published methods or in house procedures.
2. Performs preparation and analytical steps for basic laboratory methods.
3. Works under the direction of a Laboratory Analyst on complex methodologies.
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4. Assists Laboratory Analysts on preparation, analytical or data reduction steps for complex
methodologies.
5. Monitors quality control data as required or directed. This includes examination of raw data
such as chromatograms as well as an inspection of reduced data, calibration curves, and
laboratory notebooks.
1.8.12 Sample Management Personnel
1. Signs for incoming samples and verifies the data entered on the Chain-of-Custody forms.
2. Enters the sample information into the Laboratory Information Management System (LIMS)
for tracking and reporting.
3. Stages samples according to EPA requirements.
4. Assists Project Managers and Coordinators in filling bottle orders and sample shipments.
1.8.13 Systems Administrator or Systems Manager
1. Assists with the creation and maintenance of electronic data deliverables (EDDs).
2. Coordinates the installation and use of all hardware, software and operating systems.
3. Performs troubleshooting on all aforementioned systems.
4. Trains new and existing users on systems and system upgrades.
5. Maintains all system security passwords.
6. Maintains the electronic backups of all computer systems.
1.8.14 Safety/Chemical Hygiene Officer
Maintains the laboratory Chemical Hygiene Plan.
Plans and implements safety policies and procedures.
Maintains safety records.
Organizes and/or performs safety training.
Performs safety inspections and provides corrective/preventative actions.
Assists personnel with safety issues (e.g. personal protective equipment).
1.8.15 Regional Quality Manager
1. Oversees the laboratory Quality Systems of multiple laboratories or service centers while
functioning independently from laboratory operations. Reports directly to the General
Manager.
2 Monitors Quality Assurance policies and Quality Control procedures to ensure that the
laboratories achieves established standards of quality.
3 Maintains records of quality control data and evaluates data quality.
4 Conducts periodic internal audits and coordinates external audits performed by regulatory
agencies or client representatives.
5 Maintains the document control system
6 Assists in development and implementation of appropriate training programs.
7 Provides technical support to laboratory operations regarding methodology and project
QA/QC requirements.
8 Maintains certifications from federal and state programs.
9 Ensures compliance with all applicable state, federal and industry standards.
9.8 Training and Orientation
Each new employee receives a five part orientation: human resources, ethics and data integrity, safety, Quality
Systems, and departmental.
The human resources orientation includes benefits, salary, and company policies. All records are stored with
Human Resources.
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The ethics and data integrity training covers the obligations of each employee to ensure the defensibility of
laboratory data. Employees are provided with general policies related to ethics in the laboratory and specific
examples of improper practices that are unacceptable in any PASI facility. The employee is trained to make
the right decisions with regards to laboratory practices and where to go for answers in circumstances where
they may be unclear as to the correct protocol.
The safety orientation includes an in-depth review of the PASI Chemical Hygiene Plan/Safety Plan, which are
consistent with the requirements of OSHA's Hazard Communication Program (29 CFR 1910.1200) and other
pertinent regulations.
The Quality Systems orientation provides the new employee with information through an introduction to the
Quality Assurance Manual and SOPS, acceptable record keeping practices, and the individual's responsibility
to data quality. Quality Systems training is reinforced with the new employee as specific topics are covered
during the departmental or analytical method training. Quality Systems training will address policies and
practices that ensure the quality and defensibility of the analytical data. These topics include but are not
limited to traceability of measurements, method calibration, calibration verification, accuracy, precision and
uncertainty of measurements, corrective actions, documentation and root cause analysis.
The new employee's Department Supervisor provides the employee with a basic understanding of the role of
the laboratory within the structure of PASI and the basic elements of that individual's position.
Supervised training uses the following techniques:
• Hands-on training
• Training checklists
• Lectures and training sessions
• Method-specific training
• Conferences and seminars
• Short courses
• Specialized training by instrument manufacturers
• Proficiency testing programs.
Group Supervisors/Leaders are responsible for providing documentation of training and proficiency for each
employee under their supervision. The employee's training file indicates what procedures an analyst or a
technician is capable of performing, either independently or with supervision. The files also include
documentation of continuing capability (see Section 3.4 for details on Demonstration of Capability
requirements). Training documentation files for each person are kept in a central location.
All procedures and training records are maintained and available for review during laboratory audits. These
procedures are reviewed/updated annually by lab management. Additional information can be found in SOP
S-ALL-Q-020 Orientation and Training Procedures or its equivalent revision or replacement.
9.9 Laboratory Safety
It is the policy of PASI to make safety and health an integral part of daily operations and to ensure that all
employees are provided with safe working conditions, personal protective equipment, and requisite
training to do their work without injury. Each employee is responsible for his/her own safety by
complying with established company rules and procedures. These rules and procedures as well as a more
detailed description of the employees' responsibilities are contained in the corporate Safety Manual and
Chemical Hygiene Plan.
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9.10 Security and Confidentiality
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Security is maintained by controlled access to laboratory buildings. Exterior doors to laboratory buildings
remain either locked or continuously monitored by PASI staff. Keyless door-lock combinations (and
computer access codes/logins) are changed periodically. Posted signs direct visitors to the reception office and
mark all other areas as off limits to unauthorized personnel. All visitors to the facility must sign the Visitor's
Logbook maintained by the receptionist. A staff member will accompany them during the duration of their
stay on the premises unless the GM, QM or TD specify otherwise. In this instance, the staff member will
escort the visitor back to the reception area at the end of his/her visit where he/she signs out. The last staff
member to leave their department for the day should ensure that all outside access points to that area are
secure.
Additional security is provided where necessary, e.g., specific secure areas for sample, data and client report
storage, as requested by customers or cases where national security is of concern. These areas are lockable
within the facilities, or are in secure offsite storage. Access is limited to specific individuals or their designees.
Security of sample storage areas is the responsibility of the Sample Custodian. Security of samples and data
during analysis and data reduction is the responsibility of Group Supervisors. Security of client report
archives is the responsibility of the Client Services Manager. These secure areas are locked whenever these
individuals or their designees are not present in the facility.
Access to designated laboratory sample storage locations is limited to authorized personnel only. Provisions
for lock and key access are provided. No samples are to be removed without proper authorization. If
requested by client or contract, samples are not to be removed from secure storage areas without filling out the
associated internal Chain-of-Custody records.
Standard business practices of confidentiality are applied to all documents and information regarding client
analyses. Specific protocols for handling confidential documents are described in PASI SOPS. Additional
protocols for internal identification of samples and data by number only are implemented as required under
contract-specific Quality Assurance Project Plans (QAPPs).
All information pertaining to a particular client, including national security concerns will remain confidential.
Data will be released to outside agencies only with written authorization from the client or where federal or
state law requires the company to do so (i.e. federal or state subpoena).
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2.0 SAMPLE CUSTODY
2.1 Sampling Support
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Each individual PASI laboratory provides shipping containers, sample containers (including applicable
chemical preservatives), custody documents, and field quality control samples (e.g., trip blanks) to support
field-sampling events. Guidelines for sample container types, preservatives, and holding times for a
variety of methods are listed in Attachment VIII. Note that all analyses listed are not necessarily
performed at all PASI and there may be additional laboratory analyses performed that are not included in
these tables. PASI - Minnesota may provide pick-up and delivery services to their customers when
needed.
2.2 Project Initiation
Prior to accepting new work, the laboratory reviews performance capability. The laboratory establishes
that sufficient resources (personnel, equipment capacity, analytical method capability, etc.) are available
to complete the required work. The client needs and data quality objectives are defined and appropriate
environmental test methods are assured to meet client's requirements by project managers or sales
representative. Project Managers review laboratory certifications. Members of the management staff
review current instrument capacity, personnel availability and training, analytical procedures capability
and projected sample load. Management then informs the sales and client services personnel whether or
not the laboratory can accept the new project via written correspondence, email, and/or daily operations
meetings.
The laboratory maintains records of all such reviews, including discussions with customers. Routine
analytical project documentation of quotes, notes, dates, initials and/or recordings is maintained in a
project folder by project management. Conditions for new and more complex contracts are determined by
the General Managers and sales representatives. Quality Management is consulted on technical
requirements and operations staff provides input on volume capacities. Evidence of these reviews is
maintained in the form of awarded Request for Proposals (RFPs), signed quotes or contracts, and a
Customer Relationship Management (CRM) database. If a review identifies a potential mismatch between
customer requirements and laboratory capabilities and/or capacities, Pace will specify its level of
commitment by listing these exceptions to the requirements within the RFP, quote or contract.
2.3 Chain-Of-Custody
A chain-of-custody (COC) (see Attachment VII) document provides the legal documentation of samples
from time of collection to completion of analysis. Importance is stressed on completeness of COCs.
PASI has implemented Standard Operating Procedures to ensure that sample custody traceability and
responsibility objectives are achieved for every project.
Field personnel or client representatives complete a chain-of-custody form for all samples. Samples are
received by the laboratory accompanied by these forms.
If sample shipments are not accompanied by the correct documentation, the Sample Receiving department
notifies a Project Manager. The Project Manager then obtains the correct documentation/information from the
client in order for analysis of samples to proceed.
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The sampler is responsible for providing the following information on the chain-of-custody form:
• Client project name
• Project location or number
• Field sample number/identification
• Date and time sampled
• Sample type (matrix)
• Preservative
• Requested analyses
• Sampler signature
• Relinquishing signature
• Date and time relinquished
• Sampler remarks (if applicable)
• Custody Seal Number (if applicable)
• Regulatory Program Designation
• The state where the samples were collected to ensure all applicable state requirements are met
• Turnaround time requested
• Purchase order number
The record is filled out completely and legibly with indelible ink. Errors are corrected by drawing a single line
through the initial entry and initialing and dating the change. All transfers of samples are recorded on the
chain-of-custody in the "relinquished" and "received by" sections. All information except signatures is
printed.
Additional information can be found in SOP S-MN-C-001 Sample Management or its equivalent revision
or replacement.
2.4 Sample Acceptance Policy
In accordance with regulatory guidelines, PASI complies with the following sample acceptance policy for
all samples received.
If the samples do not meet the sample receipt acceptance criteria outlined below, the laboratory is required
to document all non-compliances, contact the client, and either reject the samples or fully document any
decisions to proceed with analyses of samples which do not meet the criteria. Any results reported from
samples not meeting these criteria are appropriately qualified on the final report.
All samples must:
• Have unique client identification that are clearly marked with durable waterproof labels on the sample
containers and that match the chain of custody.
• Have clear documentation on the chain of custody related to the location of the sampling site with the
time and date of sample collection.
• Have the sampler's name and signature
• Have the requested analyses clearly marked
• Have clear documentation of any special analysis requirements (data deliverables, etc.);
• Be in appropriate sample containers with clear documentation of the preservatives used.
• Be correctly preserved unless method allows for laboratory preservation.
• Be received within holding time. Any samples with hold times that are exceeded will not be
processed without prior client permission.
• Have sufficient sample volume to proceed with the analytical testing. If insufficient sample volume is
received, analysis will not proceed without client approval.
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Be received within appropriate temperature ranges - not frozen but <6°C (See Nle i) unless program
requirements or client contractual obligations mandate otherwise (see Note z) The cooler temperature is
recorded directly on the COC and the SCUR. Samples that are delivered to the lab immediately after
collection are considered acceptable if there is evidence that the chilling process has been started, for
example by the arrival of the samples on ice. If samples arrive that are not compliant with these
temperature requirements, the client will be notified. The analysis will NOT proceed unless
otherwise directed by the client. If less than 72 hours remain in the hold time for the analysis, the
analysis may be started while the client is contacted to avoid missing the hold time. Data will be
appropriately qualified on the final report.
Note 1: Temperature will be read and recorded based on the precision of the measuring device. For
example, temperatures obtained from a thermometer graduated to 0.1°C will be read and recorded to
f0.10C. Measurements obtained from a thermometer graduate to 0.5°C will be read to f0.50C.
Measurements read at the specified precision are not to be rounded down to meet the <6°C limit (i.e.
6.2°C rounded and recorded as 6°C).
Note 2: Some microbiology methods allow sample receipt temperatures of up to 10°C. Consult the
specific method for microbiology samples received above 6°C prior to initiating corrective action for
out of temperature preservation conditions.
Upon sample receipt, the following items are also checked and recorded:
• Presence of custody seals or tapes on the shipping containers
• Sample condition: Intact, broken/leaking
• Sample holding time
• Sample pH when required
• Appropriate containers
Samples for drinking water analysis that are improperly preserved, or are received past holding time, are
rejected at the time of receipt, with the exception of VOA samples that are tested for pH at the time of
analysis.
Additional information can be found in SOP S-MN-C-001 Sample Management or its equivalent revision
or replacement.
2.5 Sample Log-in
After sample inspection, all sample information on the chain-of-custody is entered into the Laboratory
Information Management System (LIMS).
This permanent record documents receipt of all sample containers including:
• Client name and contact
• Client number
• Pace Analytical project number
• Pace Analytical Project Manager
• Sample descriptions
• Due dates
• List of analyses requested
• Date and time of lab receipt
• Field ID code
• Date and time of collection
• Any comments resulting from inspection for sample rejection
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All samples received are logged into the LIMS system within one working day of receipt. Sample login may
be delayed due to client clarification of analysis needed, corrective actions for sample receipt non-
conformance, or other unusual circumstances. If the time collected for any sample is unspecified and Pace is
unable to obtain this information from the customer, the laboratory will use 00:00 as the time sampled. All
hold times will be based on this sampling time and qualified accordingly if exceeded.
The Laboratory Information Management System (EPIC Pro) automatically generates a unique identification
number for each sample created in the system. The LIMS sample number follows the general convention of
10-XXXXX-YYY. The 10 represents Minnesota as the laboratory location. The 5 digit "X" number
represents the project number followed by a 3 digit sample number. The project number is a sequential
number that is assigned as a new project is created. The sample number corresponds to the number of
samples submitted by the client. In addition to the unique sample ID, there is a sample container ID that
consists of the sample number, the container type (ex. BP IU), and bottle 1 of Y. Together the sample LIMB
number and sample container ID number create a unique barcode encryption that can be linked to the sample
analysis requested by the client. This unique identification number is placed on the sample container as a
durable label and becomes the link between the laboratory's sample management system and the client's
field identification; it will be a permanent reference number for all future interactions.
Sample labels are printed from the LIMS system and affixed to each sample container.
Samples with hold times that are near expiration date/time may be sent directly to the laboratory for analysis
at the discretion of the Project Manager and/or General Manager.
Additional information can be found in SOP S-MN-C-001 Sample Management or its equivalent revision
or replacement.
2.6 Sample Storage
2.6.1 Storage Conditions
Samples are stored away from all standards, reagents, or other potential sources of
contamination. Samples are stored in a manner that prevents cross-contamination (e.g. volatile
samples are stored separate from other samples). All sample fractions, extracts, leachates and
other sample preparation products are stored in the same manner as actual samples or as
specified by the analytical method
2.6.2 Temperature Monitoring
Samples are taken to the appropriate storage location (ambient, refrigerator, freezer) immediately
after sample receipt and check-in procedures are completed. All sample storage areas are located
in limited access areas and are monitored to ensure sample integrity.
The temperature of each refrigerated storage area is maintained at <6C unless state or program
requirements differ. The temperature of each freezer storage area is maintained at <0°C unless
state or program requirements differ. The temperature of each storage area is monitored and
recorded each workday. If the temperature falls outside the acceptable limits, the following
corrective actions are taken and appropriately documented:
• The temperature is rechecked after two hours to verify temperature exceedance. Corrective
action is initiated if necessary.
• The Quality Manager and/or laboratory management are notified if the problem persists.
• The samples are relocated to a proper environment if the temperature cannot be maintained
after corrective actions are implemented.
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• The affected customers are notified.
• Documentation is provided on analytical report.
2.6.3 Hazardous Materials
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Pure product or potentially heavily contaminated samples are tagged as "hazardous" or "lab
pack" and are stored separately from other samples.
2.6.4 Foreign/Quarantined Soils
Depending on the soil disposal practices of the laboratory, foreign soils and soils from USDA
regulated areas are segregated. The USDA requires these samples to be incinerated or sterilized
by an approved treatment procedure.
Additional information can be found in SOP MN-Q-253 Procedure for Handling of USDA Regulated
Soils or its equivalent revision or replacement.
2.7 Sample Protection
PASI laboratory facilities are operated under controlled access to ensure sample and data integrity.
Visitors must register at the front desk and be properly escorted.
Samples are removed from storage areas by designated personnel and returned to the storage areas, if
necessary, immediately after the required sample quantity has been taken.
Upon client request, additional and more rigorous chain-of-custody protocols for samples and data can be
implemented. For example, some projects may require complete documentation of sample custody within
the secure laboratory.
Additional information can be found in SOP S-MN-C-001 Sample Management or its equivalent revision
or replacement.
2.8 Subcontracting Analytical Services
Every effort is made to perform chemical analyses for PASI customers within the laboratory that receives the
samples. When subcontracting to a laboratory other than the receiving laboratory (inside or outside the PASI
network) becomes necessary, a preliminary verbal communication with an appropriate laboratory is
undertaken. Customers are notified in writing of the lab's intention to subcontract any portion of the testing to
another laboratory. Work performed under specific protocols may involve special considerations.
Prior to subcontracting samples to a laboratory outside Pace Analytical, the potential sub-contract laboratory
will be pre-qualified by verifying that the subcontractor meets the following criteria:
• All certifications required for the proposed subcontract are in effect,
• Sufficient professional liability and other required insurance coverage is in effect, and
• Is not involved in legal action by any federal, state, or local government agency for data integrity issues
and has not been convicted in such investigation at any time during the past 5 years.
The contact and preliminary arrangements are made between the PASI Project Manager and the appropriate
subcontract laboratory personnel. The specific terms of the subcontract laboratory agreement include :
Method of analysis
Number and type of samples expected
Project specific QA/QC requirements
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• Deliverables required
• Laboratory certification requirement
• Price per analysis
• Turn around time requirements
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Chain-of-custody forms are generated for samples requiring subcontracting to other laboratories. Sample
receiving personnel re-package the samples for shipment, create a transfer chain-of-custody form and
record the following information:
• Pace Analytical Laboratory Number
• Matrix
• Requested analysis
• Special instructions (quick turn-around, required detection or reporting limits, unusual information known
about the samples or analytical procedure).
• Signature in "Relinquished By"
All subcontracted sample data reports are sent to the PASI Project Manager.
Any Pace Analytical work sent to other labs within the PASI network is handled as subcontracted work (also
known as inter-regional) and all final reports are labeled clearly with the name of the laboratory performing
the work. Any non-NELAC work is clearly identified. PASI will not be responsible for analytical data if the
subcontract laboratory was designated by the Client.
Additional information can be found in SOP S-MN-C-004 Subcontracting Samples or its equivalent
revision or replacement.
2.9 Sample Retention and Disposal
Samples (and sample by-products) must be retained by the laboratory for a period of time necessary to
protect the integrity of the sample or sample by-product (e.g. method holding time) and to protect the
interests of the laboratory and the client.
Unused portions of samples are retained by each laboratory based on program or client requirements for
sample retention and storage. The sample retention time is a minimum of 45 days from receipt of the
samples. Samples requiring storage beyond this time due to special requests or contractual obligations
will not be stored under temperature controlled conditions unless the laboratory has sufficient capacity and
their presence does not compromise the integrity of other samples.
After this period expires, non-hazardous samples are properly disposed of as non-hazardous waste.
The preferred method for disposition of hazardous samples is to return the excess sample to the client. If it is
not feasible to return samples, or the client requires PASI to dispose of excess samples, PASI will arrange for
proper disposal by an approved contractor.
Additional information can be found in SOP S-ALL-S-002 Waste Handling and S-MN-C-001 Sample
Management or their equivalent revisions or replacements.
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3.0 ANALYTICAL CAPABILITIES
3.1 Analytical Method Sources
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PASI laboratories are capable of analyzing a full range of environmental samples from a variety of matrices,
including air, surface water, wastewater, groundwater, soil, sediment, biota, and other waste products. The
latest valid edition of methodologies are applied from regulatory and professional sources including EPA,
ASTM, USGS, NIOSH, and State Agencies. Section 11 (References) is a representative listing of general
analytical protocol references. PASI discloses in writing to its customers and regulatory agencies any
instances in which modified methods are being used in the analysis of samples.
In the event of a client specific need, instrumentation constraint or regulatory requirement, PASI laboratories
reserve the right to use valid versions of methods that may not be the most recent edition available.
3.2 Analytical Method Documentation
The primary form of documentation of analytical methods is the Standard Operating Procedure (SOP).
SOPS contain pertinent information as to what steps are required by an analyst to successfully perform a
procedure. The required contents for the SOPS are specified in the company-wide SOP for Preparation of
SOPS (ALL-Q-001), or equivalent revisions or replacements.
The SOPS may be supplemented by other training materials that further detail how methods are
specifically performed. This training material will undergo annual, documented review along with the
other Quality System documentation.
3.3 Analytical Method Validation
In some situations, PASI develops and validates methodologies that may be more applicable to a specific
problem or objective. When non-standard methods (e.g. methods other than EPA, NIOSH, ASTM, AOAC,
etc.) are required for specific projects or analytes of interest, or when the laboratory develops a method, or
modifies a standard method, the laboratory validates the method prior to applying it to client samples. Method
validity is established by meeting criteria for precision and accuracy as established by the data quality
objectives specified by the end user of the data. The laboratory records the validation procedure, the results
obtained and a statement as to the usability of the method. The minimum requirements for method validation
include determination of the limit of detection and limit of quantitation, evaluation of precision and bias, and
evaluation of selectivity of each analyte of interest.
Additional information can be found in SOP MN-Q-252 Methods Validation and Modification Studies, or
equivalent revisions or replacement.
3.4 Demonstration of Capability (DOC)
Analysts complete an initial demonstration of capability (IDOC) study prior to performing a method or
when there is a change in instrument type, personnel or test method (when a defined `work cell' is in
operation, the entire work cell must meet the criteria). The mean recovery and standard deviation of each
analyte, taken from 4 replicates of a quality control standard is calculated and compared to method criteria
(if available) or established lab criteria for evaluation of acceptance. Each laboratory maintains copies of
all demonstrations of capability and corresponding raw data for future reference and must document the
acceptance criteria prior to the analysis of the DOC. Demonstrations of capability are verified on an
annual basis.
Alternative demonstration of capability procedures may be used for IDOC for methods that don't lend
themselves to the "4 replicate" approach. For methods that only measure precision, the precision of four
laboratory duplicate pairs will be assessed. The relative percent differences must be within the method
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acceptance limits. For procedures like TCLP or SPLP, the analyst will demonstrate making the buffered
solution and tumbling process. The trainer or supervisor will sign-off on demonstration of capability of
the tumbling process. Additional demonstration of capability requirements will be specified in Section 14
- Method Performance of the applicable SOP.
For Continuing Demonstrations of Capability, the laboratories may use Performance Testing (PT) samples
in addition to the IDOC procedures or requirements provided in Section 14 of the applicable analytical
sops.
Pace Analytical utilizes a peer review system for data review and approval. The data review staff are
qualified to validate data conversion, transcription, and reporting in addition to assessing deviations from
the standard operating procedures. The data review staff are familiar with the analytical method
procedures with documentation maintained in their training files. The data reviewers also utilize a method
specific checklist which contains the quality control acceptance criteria. Deviations from the standard
operating procedure are documented on the checklist by the analyst. Further data review guidance is
provided in SOP MN-L-132 Data Reduction, Validation and Reporting in the Environmental Lab.
Additional information can be found in SOP S-ALL-Q-020 Orientation and Training Procedures, or
equivalent revision or replacement.
3.5 Regulatory and Method Compliance
PASI understands that expectations of our customers commonly include the assumption that laboratory data
will satisfy specific regulatory requirements. Therefore PASI attempts to ascertain, prior to beginning a
project, what applicable regulatory jurisdiction, agency, or protocols apply to that project. This
information is also required on the Chain-of-Custody submitted with samples.
PASI makes every effort to detect regulatory or project plan inconsistencies, based upon information from the
client, and communicate them immediately to the client in order to aid in the decision-making process. PASI
will not be liable if the client chooses not to follow PASI recommendations.
It is PASI policy to disclose in a forthright manner any detected noncompliance affecting the usability of data
produced by our laboratories. The laboratory will notify customers within 30 days of fully characterizing the
nature of the nonconformance, the scope of the nonconformance and the impact it may have on data usability.
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4.0 QUALITY CONTROL PROCEDURES
4.1 Data Integrity System
The data integrity system at PASI provides assurances to management that a highly ethical approach is being
applied to all planning, training and implementation of methods. Data integrity is crucial to the success of our
company and Pace Aanalytical is committed to providing a culture of quality throughout the organization. To
accomplish this goal, PASI has implemented a data integrity system that encompasses the following four
requirements:
1. A data integrity training program: standardized training is given to each new employee and a yearly
refresher is presented to all employees. Key topics within this training include:
o Need for honesty in analytical reporting
o Process for reporting data integrity issues
o Specific examples of unethical behavior and improper practices
o Documentation of non-conforming data that is still useful to the data user
o Consequences and punishments for unethical behavior
o Examples of monitoring devices used by management to review data and systems
2. Signed data integrity documentation for all employees: this includes a written quiz following the Ethics
training session and written agreement to abide by the Code of Ethics and Standards of Conduct
explained in the employee manual
3. In-depth, periodic monitoring of data integrity: including peer data review and validation, internal data
audits, proficiency testing studies, etc.
4. Documentation of any review or investigation into possible data integrity infractions. This
documentation, including any disciplinary actions involved, corrective actions taken, and notifications to
customers must be available for review for lab assessors and must be retained for a minimum of five
years.
PASI management makes every effort to ensure that personnel are free from any undue pressures that affect
the quality of their work including commercial, financial, over-scheduling and working condition pressures.
Corporate management also provides all PASI facilities a mechanism for confidential reporting of data
integrity issues that ensures confidentiality and a receptive environment in which all employees are
comfortable discussing items of ethical concern. The anonymous message line is monitored by the Corporate
Director of Quality, Safety and Technology who will ensure that all concerns are evaluated and, where
necessary, brought to the attention of executive management and investigated. The message line voice mail
box is available at 612-607-6427.
4.2 Method Blank
A method blank is used to evaluate contamination in the preparation/analysis system. The method blank
is processed through all preparation and analytical steps with its associated samples.
A method blank is processed at a minimum frequency of 1 per preparation batch. In the case of a method
that has no separate preparation step (e.g. volatiles), a method blank is processed with no more than 20
samples of a specific matrix performed by the same analyst, in the same method, using the same standards
or reagents.
The method blank consists of a matrix similar to the associated samples that is known to be free of the
analytes of interest. Laboratories will characterize a representative matrix as "clean" if the matrix
contains contaminants at less than ''/z the laboratory's reporting limit.
Each method blank is evaluated for contamination. The source of any contamination is investigated and
documented corrective action is taken when the concentration of any target analyte is detected above the
reporting limit and is greater then 1/10 of the amount of that analyte found in any associated sample.
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Corrective actions include the re-preparation and re-analysis of all the samples (where possible) along
with the full set of required quality control samples. Data qualifiers must be applied to any result reported
that is associated with a contaminated method blank.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
4.3 Laboratory Control Sample
The Laboratory Control Sample (LCS) is used to evaluate the performance of the entire analytical system
including preparation and analysis.
An LCS is processed at a minimum frequency of 1 per preparation batch. In the case of a method that has
no separate preparation step (e.g. volatiles), an LCS will be processed with no more than 20 samples of a
specific matrix performed by the same analyst, in the same method, using the same standards or reagents.
The LCS consists of a matrix similar to the associated samples that is known to be free of the analytes of
interest that is then spiked with known concentrations of target analytes.
The LCS contains all analytes specified by a specific method or by the client or regulatory agency. In the
absence of specified components, the lab will spike with the following compounds:
For multi-peak analytes (e.g. PCBs), a representative standard will be processed.
For methods with long lists of analytes, a representative number of target analytes may be
chosen. The following criteria is used to determine the number of LCS compounds used:
o For methods with 1-10 target compounds, the lab will spike with all compounds
o For methods with 11-20 target compounds, the lab will spike with at least 10
compounds or 80%, whichever is greater
o For methods with greater than 20 compounds, the lab will spike with at least 16
compounds.
The LCS is evaluated against the method default or laboratory-derived acceptance criteria. Method
default control limits will be used until the laboratory has a minimum of 20 (preferably greater than 30)
data points from which to derive internal criteria. Any compound that is outside of these limits is
considered to be `out of control' and must be qualified appropriately. Any associated sample containing
an `out-of-control' compound must either be re-analyzed with a successful LCS or reported with the
appropriate data qualifier.
For LCSs containing a large number of analytes, it is statistically likely that a few recoveries will be
outside of control limits. This does not necessarily mean that the system is out of control, and therefore no
corrective action would be necessary (except for proper documentation). NELAC has allowed for a
minimum number of marginal exceedances, defined as recoveries that are beyond the LCS control limits
(3X the standard deviation) but less than the marginal exceedance limits (4X the standard deviation). The
number of allowable exceedances depends on the number of compounds in the LCS. If more analyte
recoveries exceed the LCS control limits than is allowed (see below) or if any one analyte exceeds the
marginal exceedance limits, then the LCS is considered non-compliant and corrective actions are
necessary. The number of allowable exceedances is as follows:
• >90 analytes in the LCS- 5 analytes
• 71-90 analytes in the LCS- 4 analytes
• 51-70 analytes in the LCS- 3 analytes
• 31-50 analytes in the LCS- 2 analytes
• 11-30 analytes in the LCS- 1 analyte
• <I I analytes in the LCS- no analytes allowed out)
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A matrix spike (MS) can be used in place of a non-compliant LCS in a batch as long as the MS passes the
LCS acceptance criteria (this is a NELAC allowance). When this happens, full documentation must be
made available to the data user. If this is not allowed by a client or regulatory body, the associated
samples must be rerun with a compliant LCS (if possible) or reported with appropriate data qualifiers.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
4.4 Matrix Spike/Matrix Spike Duplicate (MS/MSD)
A matrix spike (MS) is used to determine the effect of the sample matrix on compound recovery for a
particular method. The information from these spikes is sample or matrix specific and is not used to
determine the acceptance of an entire batch (see LCS).
A Matrix Spike/Matrix Spike Duplicate (MS/MSD) set is processed at a frequency specified in a
particular method or as determined by a specific client. This frequency will be specified in the applicable
method SOP or client QAPP. In the absence of such requirements, an MS/MSD set is routinely analyzed
once per every 20 samples per general matrix (i.e. soil, water, biota, etc.) per method.
The MS and MSD consist of the sample matrix that is then spiked with known concentrations of target
analytes. Lab personnel spike client samples that are specifically designated as MS/MSD samples or,
when no designated samples are present in a batch, randomly select samples to spike that have adequate
sample volume or weight. Spiked samples are prepared and analyzed in the same manner as the original
samples and are selected from different customers if possible.
The MS and MSD contain all analytes specified by a specific method or by the client or regulatory
agency. In the absence of specified components, the lab will spike with the same number of compounds
as previously discussed in the LCS section.
The MS and MSD are evaluated against the method or laboratory-derived criteria. Any compound that is
outside of these limits is considered to be `out of control' and must be qualified appropriately. Batch
acceptance, however, is based on method blank and LCS performance, not on MS/MSD recoveries. The
spike recoveries give the data user a better understanding of the final results based on their site-specific
information.
A matrix spike and sample duplicate will be performed instead of a matrix spike and matrix spike
duplicate when specified by the client or method.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
4.5 Surrogates
Surrogates are compounds that reflect the chemistry of target analytes and are typically added to samples
for organic analyses to monitor the effect of the sample matrix on compound recovery.
Surrogates are added to each client sample (for organics), method blank, LCS and MS prior to extraction
or analysis. The surrogates are evaluated against the method or laboratory-derived acceptance criteria.
Any surrogate compound that is outside of these limits is considered to be `out of control' and must be
qualified appropriately. Samples with surrogate failures are typically re-extracted and/or re-analyzed to
confirm that the out-of-control value was caused by the matrix of the sample and not by some other
systematic error. An exception to this would be samples that have high surrogate values but no reportable
hits for target compounds. These samples would be reported, with a qualifier, because the implied high
bias would not affect the final results.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
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4.6 Sample Duplicate
A sample duplicate is a second portion of sample that is prepared and analyzed in the laboratory along
with the first portion. It is used to measure the precision associated with preparation and analysis. A
sample duplicate is processed at a frequency specified by the particular method or as determined by a
specific client.
The sample and duplicate are evaluated against the method or laboratory-derived criteria for relative
percent difference (RPD). Any duplicate that is outside of these limits is considered to be `out of control'
and must be qualified appropriately.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
4.7 Internal Standards
Internal Standards are method-specific analytes added to every standard, method blank, laboratory control
sample, matrix spike, matrix spike duplicate, and sample at a known concentration, prior to analysis for
the purpose of adjusting the response factor used in quantifying target analytes. At a minimum, the
laboratory will follow method specific guidelines for the treatment of internal standard recoveries as they
are related to the reporting of data.
Deviations made from this policy must be approved by the Quality Manager prior to release of the data.
4.8 Field Blanks
Field blanks are blanks prepared at the sampling site in order to monitor for contamination that may be
present in the environment where samples are collected. These field quality control samples are often
referenced as field blanks, rinseate blanks, or equipment blanks. The lab analyzes these field blanks as
normal samples and informs the client if there are any target compounds detected above the reporting
limits.
4.9 Trip Blanks
Trip blanks are blanks that originate from the laboratory as part of the sampling event and are used to
monitor for contamination of samples during transport. These blanks accompany the empty sample
containers to the field and then accompany the collected samples back to the lab. These blanks are
routinely analyzed for volatile methods where ambient background contamination is likely to occur.
4.10 Limit of Detection (LOD)
PASI laboratories are required to use a documented procedure to determine a limit of detection (LOD) for
each analyte of concern in each matrix reported. All sample-processing steps of the preparation and
analytical methods are included in this determination. For any test that does not have a valid LOD,
sample results below the lowest calibration standard cannot be reported.
The LOD is initially established for the compounds of interest for each method in a clean matrix with no
target analytes present and no interferences at a concentration that would impact the results. The LOD is
then determined every time there is a change in the test method that affects how the test is performed or
when there has been a change in the instrument that affects the sensitivity. The LOD is, at a minimum,
verified on an annual basis. If required by client or accreditation body, the LOD will be reestablished
annually for all applicable methods.
Unless otherwise noted, the method used by PASI laboratories to determine LODs is based on the Method
Detection Limit (MDL) procedure outlined in 40 CFR Part 136, Appendix B. Where required by
regulatory program or client, the above referenced procedure will be followed.
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Additional information can be found in SOP S-ALL-Q-004 Method Detection Limit Studies or its
equivalent revision or replacement.
4.11 Limit of Quantitation (LOQ)
A limit of quantitation (LOQ) for every analyte of concern must be determined. For PASI laboratories,
this LOQ is referred to as the PRL, or Pace Reporting Limit. This PRL is based on the lowest calibration
standard concentration that is used in each initial calibration. Results below this level are not allowed to
be reported without qualification since the results would not be substantiated by a calibration standard.
For methods with a determined LOD, results can be reported out below the LOQ but above the LOD if
they are properly qualified (e.g. J flag).
There must be a sufficient buffer between the LOD and the limit of quantitation (LOQ). The LOQ must
be higher than the LOD.
To verify the LOQ, the laboratory will prepare a sample in the same matrix used for the LCS. The sample
will be spiked with target analytes at the concentration(s) equivalent to or less than the PRL(s). This
sample must undergo the routine sample preparation procedure including any routine sample cleanup
steps. The sample is then analyzed and the recovery of each target analyte determined. The recovery for
each target analyte must meet the laboratories current control limits.
Additional information can be found in SOP S-ALL-Q-004 Method Detection Limit Studies or its
equivalent revision or replacement.
4.12 Estimate of Uncertainty
PASI laboratories can provide an estimation of uncertainty for results generated by the laboratory. The
estimate quantifies the error associated with any given result at a 95% confidence interval. This estimate
does not include bias that may be associated with sampling. The laboratory has a procedure in place for
making this estimation. In the absence of a regulatory or client specific procedure, PASI laboratories base
this estimation on the recovery data obtained from the Laboratory Control Spikes. The uncertainty is a
function of the standard deviation of the recoveries multiplied by the appropriate Student's t Factor at 95%
confidence. Additional information pertaining to the estimation of uncertainty and the exact manner in
which it is derived are contained in the SOP MN-Q-255 or its equivalent revision or replacement.
The measurement of uncertainty is provided only on request by the client, as required by specification or
regulation and when the result is used to determine conformance within a specification limit.
4.13 Proficiency Testing (PT) Studies
PASI laboratories participate in the NELAC-defined proficiency testing program. PT samples are
obtained from NIST-approved providers and analyzed and reported at a minimum of two times per year
for the relevant fields of testing per matrix.
The lab initiates an investigation whenever PT results are deemed `unacceptable' by the PT provider. All
findings and corrective actions taken are reported to the Quality Manager. A corrective action plan
(including re-analysis of similar samples) is initiated and this report is sent to the appropriate state
accreditation agencies for their review.
PT samples are treated as typical client samples, utilizing the same staff, methods, equipment, facilities,
and frequency of analysis. PT samples are included in the laboratory's normal analytical processes and do
not receive extraordinary attention due to their nature.
Comparison of analytical results with anyone participating in the same PT study is prohibited prior to the
close of the study.
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Additional information can be found in SOP S-ALL-Q-010 PE/PT Program or its equivalent revision or
replacement.
4.14 Rounding and Significant Figures
In general, the PASI laboratories report data to no more than three significant digits. Therefore, all
measurements made in the analytical process must reflect this level of precision. In the event that a
parameter that contributes to the final result has less than three significant figures of precision, the final
result must be reported with no more significant figures than that of the parameter in question.
Rounding
PASI-Minnesota follows the odd / even guidelines for rounding numbers.
If the figure following the one to be retained is less than five, that figure is dropped and the retained
ones are not changed (with three significant figures, 2.544 is rounded to 2.54).
If the figure following the ones to be retained is greater than five, that figure is dropped and the last
retained one is rounded up (with three significant figures, 2.546 is rounded to 2.55).
If the figure following the ones to be retained is five and if there are no figures other than zeros
beyond that five, then the five is dropped and the last figure retained is unchanged if it is even and
rounded up if it is odd (with three significant figures, 2.525 is rounded to 2.52 and 2.535 is rounded to
2.54).
Significant Digits
Unless specified by federal, state or local requirements or on specific request by a customer, PASI-
Minnesota reports all analytical results to 3 significant digits, regardless of the magnitude of the value
reported.
PASI-Minnesota follows the following convention for reporting to a specified number of significant
figures. Unless specified by federal, state or local requirements or on specific request by a customer, the
laboratory reports:
Values > 10 - Reported to 3 significant digits
Values < 10 - Reported to 2 significant digits
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DOCUMENT MANAGEMENT AND CHANGE CONTROL
5.1 Document Management
Additional information can be found in SOP S-ALL-Q-002 Document Management.
Pace Analytical Services, Inc. has an established procedure for managing documents that are part of the
quality system. The list of managed documents includes, but is not limited to, Standard Operating
Procedures, Quality Assurance Manuals, quality policy statements, training documents, work-processing
documents, charts, posters, memoranda, notices, forms, software, and any other procedures, tables, plans,
etc. that have a direct bearing on the quality system.
A master list of all managed documents is maintained at each facility identifying the current revision
status and distribution of the controlled documents. This establishes that there are no invalid or obsolete
documents in use in the facility. All documents are reviewed periodically and revised if necessary.
Obsolete documents are systematically discarded or archived for audit or knowledge preservation
purposes.
Each managed document is uniquely identified to include the date of issue, the revision identification,
page numbers, the total number of pages and the issuing authorities. For complete information on
document numbering, refer to SOP S-ALL-Q-003 Document Numbering.
As an alternative to the hard copy system of controlled documents, secured electronic copies of controlled
documents may be maintained on the local or wide-area network (LAN or WAN). These document files
must be read-only for all personnel except the Quality Department and system administrator. Other
requirements for this system are as follows:
• Electronic documents must be readily accessible to all facility employees.
• Electronic documents must explicitly indicate that copies are not to be printed from the electronic file.
All hardcopy SOPS must be obtained from the Quality Assurance Department.
5.1.1 Quality Assurance Manual (QAM)
The Quality Assurance Manual is the company-wide document that describes all aspects of the
quality system for PASL The base QAM template is distributed by the Corporate Quality
Department to each of the regional Quality Managers. The regional management personnel
modify the necessary and pennissible sections of the base template and submit those
modifications to the Corporate Director of Quality for review. Once approved and signed by
both the CEO and the Director of Quality, the General Manager, Quality Manager and Technical
Director(s) sign the Quality Assurance Manual. Each regional Quality Manager is then in charge
of distribution to employees, external customers or regulatory agencies and maintaining a
distribution list of controlled document copies. The Quality Assurance Manual template is
reviewed on an annual basis by all of the PASI Quality Managers and revised accordingly by the
Director of Quality, Safety and Technology.
5.1.2 Standard Operating Procedures (SOPs)
SOPS fall into two categories: company-wide documents (starting with the prefix ALL-) and
facility-specific documents (starting with the individual facility prefix).
The purpose of the company-wide (ALL) SOPS is to establish policies and procedure that are
common and applicable to all PASI facilities. Company-wide (ALL) SOPS are document-
controlled by the corporate quality office and signed copies are distributed to each of the regional
Quality Managers. The regional management personnel sign the company-wide (ALL) SOPS.
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The regional Quality Manager is then in charge of distribution to employees, external customers
or regulatory agencies and maintaining a distribution list of controlled document copies.
Regional PASI facilities are responsible for developing facility-specific SOPS applicable to their
respective facility. The regional facility develops these facility-specific SOPS based on the
corporate-wide (ALL) SOP template. This template is written to incorporate a set of minimum
method requirements and PASI best practice requirements. The regional facilities may add to or
modify the corporate-wide (ALL) SOP template provided there are no contradictions to the
minimum method or best practice requirements. Facility-specific SOPS are controlled by the
regional Quality Manager according to the corporate document management policies.
SOPS are reviewed every year at a minimum (a more frequent review may be required by state or
federal agencies or customers). A review of the document does not necessarily constitute a re-
issue of a new revision. Documentation of this review and any applicable revisions are made in
the last section of each SOP. This provides a historical record of all revisions.
All copies of superseded SOPS are removed from general use and the original copy of each SOP
is archived for audit or knowledge preservation purposes. This ensures that all PASI employees
use the most current version of each SOP and provides the Quality Manager with a historical
record of each SOP.
Additional information can be found in SOP S-ALL-Q-001 Preparation of SOPS or its equivalent
revision or replacement.
5.1.3 Other Documentation
Additional documents such as Forms and Spreadsheets are controlled through the document
management system.
5.2 Document Change Control
Changes to managed documents are reviewed and approved in the same manner as the original review.
Any revision to a document requires the approval of the applicable signatories. After revisions are
approved, a revision number is assigned and the previous version of the document is officially retired.
Copies may be kept for audit or knowledge preservation purposes.
All controlled copies of the previous document are replaced with controlled copies of the revised
document and the superseded copies are destroyed or archived. All affected personnel are advised that
there has been a revision and any necessary training is scheduled.
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6.0 EQUIPMENT AND MEASUREMENT TRACEABILITY
Each PASI facility is equipped with sufficient instrumentation and support equipment to perform the
relevant analytical testing or field procedures performed by each facility. Support equipment includes
chemical standards, thermometers, balances, disposable and mechanical pipettes, etc. This section details
some of the procedures necessary to maintain traceability and perform proper calibration of
instrumentation and support equipment.
6.1 Standards and Traceability
Each PASI facility retains all pertinent information for standards, reagents and chemicals to assure
traceability to a national standard. This includes documentation of purchase, receipt, preparation and use.
Upon receipt, all purchased standard reference materials are recorded into a standard logbook or database
and assigned a unique identification number. The entries include the facility's unique identification
number, the chemical name, manufacturer name, manufacturer's identification numbers, receipt date and
expiration date. Vendor's certificates of analysis for all standards, reagents, or chemicals are retained for
future reference.
Subsequent preparations of intermediate or working solutions are also documented in a standard logbook
or database. These entries include the stock standard name and lot number, the manufacturer name, the
solvents used for preparation, the solvent lot number and manufacturer, the preparation steps, preparation
date, expiration dates, preparer's initials, and a unique PASI identification number. This number is used
in any applicable sample preparation or analysis logbook so the standard can be traced back to the
standard preparation record. This process ensures traceability back to the national standard.
All prepared standard or reagent containers include the PASI identification number, the standard or
chemical name, the date of preparation, the date of expiration, the concentration with units, and the
preparer's initials. This ensures traceability back to the standard preparation logbook.
If a second source standard is required to verify an existing calibration or spiking standard, this standard is
purchased from a different supplier. If no second source is available, a second standard from a different
lot may be purchased from the same supplier if the lot can be demonstrated as prepared independently
from other lots.
Additional information concerning standards and reagent traceability can be found in the SOP S-ALL-Q-
025 Standard and Reagent Preparation and Traceability or its equivalent revision or replacement.
6.2 General Analytical Instrument Calibration Procedures
All types of support equipment and instrumentation are calibrated or checked before use to ensure proper
functioning and verify that the laboratory's requirements are met. All calibrations are performed by, or under
the supervision of, an experienced analyst at scheduled intervals against either certified standards traceable to
recognized national standards or reference standards whose values have been statistically validated.
Calibration standards for each parameter are chosen to establish the linear range of the instrument and must
bracket the concentrations of those parameters measured in the samples. The lowest calibration standard is the
lowest concentration for which quantitative data may be reported. Data reported below this level is considered
to have less certainty and must be reported using appropriate data qualifiers (e.g. J flag) or explained in a
narrative. The Minnesota Department Health requires that the reporting limit be verified upon initial
calibration and monthly there after. The reporting limit verification must be within f 40% of the true value of
the reporting limit standard. The reporting limit may need to be adjusted accordingly to meet this criteria..
The highest calibration standard is the highest concentration for which quantitative data may be reported.
Data reported above this level is considered to have less certainty and must be reported using appropriate data
qualifiers (e.g. E flag) or explained in the narrative. Any specific method requirement for number and type of
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calibration standards supersedes the general requirement. Instrument and method specific calibration criteria
are explained within the specific analytical standard operating procedures for each facility.
Instrumentation or support equipment that cannot be calibrated to specification or is otherwise defective is
clearly labeled as out-of-service until it has been repaired and tested to demonstrate it meets the laboratory's
specifications. All repair and maintenance activities including service calls are documented in the
maintenance log. Equipment sent off-site for calibration testing is packed and transported to prevent breakage
and is in accordance with the calibration laboratory's recommendations.
In the event that recalibration of a piece of test equipment casts doubt on the validity of test results already
transmitted to the client, the client is notified in writing by the laboratory within 3 business days from the time
of discovery. This allows for sufficient investigation and review of documentation to determine the impact on
the analytical results. Instrumentation found to be consistently out of calibration is either repaired and
positively verified or replaced.
Raw data records are retained to document equipment performance. Sufficient raw data is retained to
reconstruct the instrument calibration and explicitly connect the continuing calibration verification to the
initial calibration.
6.2.1 General Organic Calibration Procedures
Calibration standards are prepared at a minimum of five concentrations for organic analyses.
Results from all calibration standards must be included in constructing the calibration curve with the
following exceptions:
• The lowest level calibration standard may be removed from the calibration as long as the
remaining number of concentration levels meets the minimum established by the method and
standard operating procedure. For multi-parameter methods, this may be done on an individual
analyte basis. The reporting limit must be adjusted to the lowest concentration included in the
calibration curve.
• The highest level calibration standard may be removed from the calibration as long as the
remaining number of concentration levels meets the minimum established by the method and
standard operating procedure. For multi-parameter methods, this may be done an individual
analyte basis. The upper limit of quantitation must be adjusted to the highest concentration
included in the calibration curve.
• Multiple points from either the high end or the low end of the calibration curve may be excluded
as long as the remaining points are contiguous in nature and the minimum number of levels
remain as established by method or standard operating procedure. The reporting limit or
quantitation range, which is appropriate, must be adjusted accordingly.
• Results from a concentration level between the lowest and highest calibration levels can be
excluded from the calibration curve for an acceptable cause with approval from the responsible
department supervisor if the results for all analytes are excluded and the point is replaced by re-
analysis. Re-analysis must occur within the same 12 hour time time period for GC/MS
methodologies and within 8 hours of the initial analysis for non-GC/MS methodologies. All
samples analyzed prior to the re-analyzed calibration curve point must be re-analyzed after the
calibration curve is completed.
Initial calibration curves are evaluated against appropriate statistical models as required by the
analytical methods. Curves that do not meet the appropriate criteria require corrective action that
may include re-nrnning the initial calibration curve. All initial calibrations are verified with a
standard obtained from a second manufacturer or second lot from the same manufacturer if the lot
can be demonstrated as prepared independently from other lots prior to the analysis of samples.
Sample results are quantitated from the initial calibration unless otherwise required by regulation,
method, or program.
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The calibration curve is periodically verified by the analysis of a mid-level continuing calibration
verification (CCV) standard during the course of sample analysis. Calibration verification is
performed at the beginning and end of each analytical batch (except if an internal standard is used
only one verification at the beginning of the batch is needed), whenever it is expected that the
analytical system may be out of calibration, if the time period for calibration has expired, or for
analytical systems that contain a calibration verification requirement. This verification standard must
meet acceptance criteria in order for sample analysis to proceed.
In the event that the CCV does not meet the acceptance criteria, a second CCV may be injected as
part of the diagnostic evaluation and corrective action investigation. If the second CCV is
acceptable, the analytical sequence is continued. If both CCVs fail, the analytical sequence is
terminated. All samples analyzed since the last compliant CCV are re-analyzed for methodologies
utilizing external calibration.
When instruments are operating unattended, the autosamplers may be programmed to inject
consecutive CCVs as a preventative measure against CCV failure with no corrective action. In this
case, both CCVs must be evaluated to determine potential impact to the results. A summary of the
decision tree and necessary documentation are listed below:
• If both CCVs meet the acceptance criteria, the analytical sequence is allowed to continue
without corrective action. (The 12 hour clock begins with the injection of the second CCV.)
• If the first CCV does not meet the acceptance criteria and the second CCV is acceptable, the
analytical sequence is continued and the results are reported.
• If the first CCV meets the acceptance criteria and the second CCV is out of control, the samples
preceded by the out of control CCV must be re-analyzed in a compliant analytical sequence.
• If both CCVs are out of control, all samples since the last acceptable CCV must be re-analyzed
in a compliant analytical sequence.
Some analytical methods require that samples be bracketed by passing CCVs analyzed both before
and after the samples. This is specific to each method but, as a general mle, all external calibration
methods require bracketing CCVs. Most internal standard calibrations do not require bracketing
CCVs.
Some analytical methods require verification based on a time interval; some methods require a
frequency based on an injection interval. The type and frequency of the calibration verifications is
dependent on both the analytical method and possibly on the quality program associated with the
samples. The type and frequency of calibration verification will be documented in the method
specific SOP employed by each laboratory.
6.2.2 General Inorganic Calibration Procedures
The instrument is initially calibrated with standards at multiple concentrations to establish the
linearity of the instrument's response. A calibration blank is also included. Initial calibration curves
are evaluated against appropriate statistical models as required by the analytical methods. The
number of calibration standards used depends on the specific method criteria or client project
requirements, although normally a minimum of three standards is used.
The ICP and ICP/MS can be standardized with a zero point and a single point calibration if:
• Prior to analysis, the zero point and the single point calibration are analyzed and a linear range is
established,
• Zero point and single point calibration standards are analyzed with each batch
• A standard corresponding to the Reporting Limit/LOQ is analyzed with the batch and meets the
established acceptance criteria
• The linearity is verified at the frequency established by the method or manufacturer.
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All initial calibrations are verified with a standard obtained from a second manufacturer or second lot
from the same manufacturer if the lot can be demonstrated as prepared independently from other lots
prior to the analysis of samples. Sample results are quantitated from the initial calibration unless
otherwise required by regulation, method, or program.
During the course of analysis, the calibration curve is periodically verified by the analysis of
calibration verification standards. A calibration verification standard is analyzed within each
analytical batch at method/program specific intervals to verify that the initial calibration is still valid.
The CCV is also analyzed at the end of the analytical batch
A calibration blank is also analyzed with each calibration verification standard to verify the
cleanliness of the system. All reported results must be bracketed by acceptable CCVs and CCBs.
Instrument and method specific calibration acceptance criteria are explained within the specific
analytical standard operating procedures for each facility.
Interference check standards are also analyzed per method requirements and must meet acceptance
criteria for metals analyses.
6.3 Support Equipment Calibration Procedures
All support equipment is calibrated or verified at least annually using NIST traceable references over the entire
range of use. The results of calibrations or verifications must be within the specifications required or the
equipment will be removed from service until repaired. The laboratory maintains records to demonstrate the
correction factors applied to working thermometers.
Prior to use on each working day, balances, ovens, refrigerators, freezers, and water baths are checked in the
expected use range with NIST traceable references in order to ensure the equipment meets laboratory
specifications.
6.3.1 Analytical Balances
Each analytical balance is checked and calibrated annually by a qualified service technician. The
calibration of each balance is checked each day of use with weights traceable to NIST.
Calibration weights are ASTM Class 1 (replaces Class S designation) and are re-certified
annually against a NIST traceable reference. Some accrediting agencies may require more
frequent checks. If balances are calibrated by an external agency, verification of their weights
must be provided. All information pertaining to balance maintenance and calibration is recorded
in the individual balance logbook and/or is maintained on file in the Quality department.
6.3.2 Thermometers
Certified, or reference, thermometers are maintained for checking calibration of working
thermometers. Reference thermometers are provided with NIST traceability for initial calibration
and are re-certified, at a minimum yearly with equipment directly traceable to NIST.
Working thermometers are compared with the reference thermometers annually according to
corporate metrology procedures. Each thermometer is individually numbered and assigned a
correction factor based on the NIST reference source. In addition, working thermometers are
visually inspected by laboratory personnel prior to use and temperatures are documented.
Laboratory thermometer inventory and calibration data are maintained in the Quality department.
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The meter is calibrated before use each day, and once after each four hours of continuous use using
fresh buffer solutions.
6.3.4 Spectrophotometers
During use, spectrophotometer performance is checked at established frequencies in analysis
sequences against initial calibration verification (ICV) and continuing calibration verification (CCV)
standards.
6.3.5 Mechanical Volumetric Dispensing Devices
Mechanical volumetric dispensing devices including bottle top dispensers, pipettes, and burettes,
excluding Class A volumetric glassware, are checked for accuracy on a quarterly basis. Non-Class A
glassware and disposable pipettes must be calibrated once per lot prior to first use. The accuracy of
glass microliter syringes is verified and documented prior to use.
Additional information regarding calibration and maintenance of laboratory support equipment can be
found in SOP ALL-Q-013 Support Equipment.
6.4 Instrument/ Equipment Maintenance
The objectives of the Pace Analytical maintenance program are twofold: to establish a system of
instrument care that maintains instrumentation and equipment at required levels of calibration and
sensitivity, and to minimize loss of productivity due to repairs.
The Laboratory Operations Manager and department manager/supervisors are responsible for providing
technical leadership to evaluate new equipment, solve equipment problems and coordinate instrument repair
and maintenance. The analysts have a primary responsibility to perform routine maintenance.
To minimize downtime and interruption of analytical work, preventative maintenance is routinely
performed on each analytical instrument. Up-to-date instructions on the use and maintenance of
equipment are available to staff in the department where the equipment is used.
Department manager/supervisors are responsible for maintaining an adequate inventory of spare parts
required to minimize equipment downtime. This inventory includes parts and supplies that are subject to
frequent failure, have limited lifetimes, or cannot be obtained in a timely manner should a failure occur.
All major equipment and instrumentation items are uniquely identified to allow for traceability.
Equipment/instrumentation are, unless otherwise stated, identified as a system and not as individual pieces.
The laboratory maintains equipment records that include the following:
• The name of the equipment and its software
• The manufacturer's name, type, and serial number
• Approximate date received and date placed into service
• Current location in the laboratory
• Condition when received (new, used, etc.)
• Copy of any manufacturer's manuals or instructions
• Dates and results of calibrations and next scheduled calibration (if known)
• Details of past maintenance activities, both routine and non-routine
• Details of any damage, modification or major repairs
All instrument maintenance is documented in maintenance logbooks that are assigned to each particular
instrument or system.
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When maintenance is performed to repair an instrument problem, depending on the initial problem,
demonstration of return to control may be satisfied by the successful analysis of a reagent blank or
continuing calibration standard. The entry must include a summary of the results of that analysis and
verification by the analyst that the instrument has been returned to an in-control status. In addition, each
entry must include the initials of the analyst making the entry, the dates the maintenance actions were
performed, and the date the entry was made in the maintenance logbook, if different from the date(s) of
the maintenance.
Any equipment that has been subjected to overloading or mishandling, or that gives suspect results, or has
been shown to be defective, is taken out of service and clearly identified. The equipment shall not be used
to analyze client samples until it has been repaired and shown to perform satisfactorily.
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7.0 CONTROL OF DATA
Analytical results processing, verification and reporting are procedures employed that result in the delivery of
defensible data. These processes include, but are not limited to, calculation of raw data into final concentration values,
review of results for accuracy, evaluation of quality control criteria and assembly of technical reports for delivery to the
data user.
All analytical data undergo a well-defined, well-documented multi-tier review process prior to being reported to the
customer. This section describes procedures used by PASI for translating raw analytical data into accurate, final sample
reports and PASI data storage policies.
7.1 Analytical Results Processing
When analytical, field, or product testing data is generated, it is either recorded in a bound laboratory
logbook (e.g. Run log or Instrument log) or copies of computer-generated printouts are appropriately
labeled and filed. These logbooks and other laboratory records are kept in accordance with each facility's
Standard Operating Procedure for documentation storage and archival.
The primary analyst is responsible for initial data reduction and review. This includes confirming
compliance with required methodology, verifying calculations, evaluating quality control data, noting
discrepancies in logbooks and as footnotes or narratives, and uploading analytical results into the LIMS.
The primary analyst then compiles the initial data package for verification. This compilation must include
sufficient documentation for data review. It may include standard calibrations, chromatograms, manual
integration documentation, electronic printouts, chain-of-custody forms, and logbook copies.
Some agencies or customers require different levels of data reporting. For these special levels, the
primary analyst may need to compile additional project information, such as initial calibration data or
extensive spectral data, before the data package proceeds to the verification step.
7.2 Data Verification
Data verification is the process of examining data and accepting or rejecting it based on pre-defined criteria.
This review step is designed to ensure that reported data are free from calculation and transcription errors, that
quality control parameters are evaluated and that any discrepancies are properly documented.
Analysts performing the analysis and subsequent data reduction have primary responsibility for quality of the
data produced. The primary analyst initiates the data verification process by reviewing and accepting the data,
provided QC criteria have been met for the samples being reported. Data review checklists are used to
document the data review process. The primary analyst is responsible for the initial input of the data into the
LIMS.
The completed data package is then sent to a designated qualified reviewer (this cannot be the primary
analyst). The following criteria have been established to qualify someone as a data reviewer. To perform
secondary data review, the reviewer must :
1. Have a current Demonstration of Capability (DOC) study on file and they have an SOP Acknowledgment
form on file for the method/procedure being reviewed.; ors" N't'
2. Have a DOC on file for a similar method/technology (i.e. GC/MS) and they have an SOP
Acknowledgment form on file for the method/procedure being reviewed; or. see Note
3. Supervise or manage a Department and have an SOP Acknowledgment form on file for the
method/procedure being reviewed; or
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4. Have significant background in the department/methods being reviewed through education or experience
and have an SOP Acknowledgment form on file for the method/procedure being reviewed
Note: Secondary reviewer status must be approved personally by the Quality Manager or General Manager in
the event that this person has no prior experience on the specific method or general technology (i.e. GUMS).
This reviewer provides an independent technical assessment of the data package and technical review for
accuracy according to methods employed and laboratory protocols. This assessment involves a quality control
review for use of the proper methodology and detection limits, compliance to quality control protocol and
criteria, presence and completeness of required deliverables, and accuracy of calculations and data
quantitation. The reviewer also validates the data entered into the LIMS.
Once the data have been technically reviewed and approved, authorization for release of the data from the
analytical section is indicated by initialing and dating the data review checklist or otherwise initialing and
dating the data. The Operations or Project Manager examines the report for method appropriateness, detection
limits and QC acceptability. Any deviations from the referenced methods are checked for documentation and
validity, and QC corrective actions are reviewed for successful resolution.
7.3 Data Reporting
All data segments pertaining to a particular PASI project number are delivered to the Client Services
Department (Project Manager) for assembly into the final report All points mentioned during technical and
QC reviews are included in a case narrative if there is potential for data to be impacted.
Final reports are prepared according to the level of reporting required by the client. A standard PASI final
report consists of the following components:
1. A title which designates the report as "Final Report", "Laboratory Results", "Certificate of Results", etc.
2. Name and address of laboratory (or subcontracted laboratories, if used).
3. Phone number and name of laboratory contact where questions can be referred.
4. A unique number for the report (project number). The pages of the report shall be numbered and a total
number of pages shall be indicated (usually in the cover letter).
5. Name and address of client and name of project (if applicable).
6. Unique identification of samples analyzed (including client sample numbers).
7. Identification of any sample that did not meet acceptable sampling requirements (from NELAC or other
governing agency), such as improper sample containers, holding times missed, sample temperature, etc.
8. Date and time of collection of samples, date of sample receipt by the laboratory, dates of sample
preparation and analysis, and times of sample preparation and analysis when the holding time for either is
72 hours or less.
9. Identification of the test methods used.
10. Identification of sampling procedures if sampling was conducted by the laboratory.
11. Deviations from, additions to, or exclusions from the test methods. These can include failed quality
control parameters, deviations caused by the matrix of the sample, etc., and can be shown as a case
narrative or as defined footnotes to the analytical data.
12. Identification of whether calculations were performed on a dry or wet-weight basis.
13. Reporting limits used.
14. Final results or measurements, supported by appropriate chromatograms, charts, tables, spectra, etc.
15. A signature and title of person accepting responsibility for the content of the report (can be an equivalent
electronic identification) and date report was issued.
16. A statement clarifying that the results of the report relate only to the samples tested or to the samples as
they were received by the laboratory.
17. If necessary, a statement indicating that the report must not be reproduced except in full, without the
written approval of the laboratory.
18. Identification of all test results provided by a subcontracted laboratory or other outside source.
19. Identification of results obtained outside of quantitation levels.
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Any changes made to a final report shall be designated as "Revised" or equivalent wording. The laboratory
must keep sufficient archived records of all lab reports and revisions. For higher levels of data deliverables, a
copy of all applicable raw data is sent to the client along with a final report of results. When possible, the
PASI facility will provide electronic data deliverables (EDD) as required by contracts or upon client request.
Client data that requires transmission by telephone, telex, facsimile or other electronic means undergoes
appropriate steps to preserve confidentiality.
Additional information on data reduction and validation can be found in SOP MN-L-132 Data Reduction,
Validation and Reporting, or equivalent replacement
7.4 Data Security
All data including electronic files, logbooks, extraction/digestion/distillation worksheets, calculations, project
files and reports, and other information used to produce the technical report are maintained secured and
retrievable by the PASI facility.
7.5 Data Archiving
All records compiled by PASI are maintained legible and retrievable and stored secured in a suitable
environment to prevent loss, damage, or deterioration by fire, flood, vermin, theft, and/or environmental
deterioration. Records are retained for a minimum of five years unless superseded by federal, state,
contractual, and/or accreditation requirements. These records may include, but are not limited to, client
data reports, calibration and maintenance of equipment, raw data from instrumentation, quality control
documents, observations, calculations and logbooks. These records are retained in order to provide for
possible historical reconstruction including sampling, receipt, preparation, analysis and personnel
involved. NELAP-related records will be made readily available to accrediting authorities. Access to
archived data is documented and controlled by the Quality Manager or a designated Data Archivist.
Records that are computer-generated have either a hard copy or electronic write-protected backup copy.
Hardware and software necessary for the retrieval of electronic data is maintained with the applicable
records. Archived electronic records are stored protected against electronic and/or magnetic sources.
In the event of a change in ownership, accountability or liability, reports of analyses performed pertaining
to accreditation will be maintained by the acquiring entity for a minimum of five years. In the event of
bankruptcy, laboratory reports and/or records will be transferred to the client and/or the appropriate
regulatory entity upon request.
7.6 Data Disposal
Data that has been archived for the facility's required storage time may be disposed of in a secure manner
by shredding, returning to customer, or utilizing some other means that does not jeopardize data
confidentiality. Records of data disposal will be archived for a minimum of five years unless superseded
by federal, contractual, and/or accreditation requirements.
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8.0 QUALITY SYSTEM AUDITS AND REVIEWS
8.1 Internal Audits
8.1.1 Responsibilities
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The Quality Manager is responsible for designing and/or conducting internal audits in accordance
with a predetermined schedule and procedure. Since internal audits represent an independent
assessment of laboratory functions, the auditor must be functionally independent from laboratory
operations to ensure objectivity. The auditor must be trained, qualified and familiar enough with
the objectives, principles, and procedures of laboratory operations to be able to perform a thorough
and effective evaluation. The Quality Manger evaluates audit observations and verifies the
completion of corrective actions. In addition, a periodic corporate audit will be conducted by the
Director of Quality, Safety & Technology and/or designee. The corporate audits will focus on the
execution of the Quality System as outlined in this manual but may also include other quality
programs applicable to each laboratory.
8.1.2 Scope and Frequency of Internal Audits
Internal systems audits are conducted yearly at a minimum. The scope of these audits includes
evaluation of specific analytical departments or a specific quality-related system as applied
throughout the laboratory.
Examples of system-wide elements that can be audited include:
• Quality Systems documents, such as Standard Operating Procedures, training documents,
Quality Assurance Manual and all applicable addenda
• Personnel and training files.
• General laboratory safety protocols.
• Chemical handling practices, such as labeling of reagents, solutions, standards, and associated
documentation.
• Documentation concerning equipment and instrumentation, calibration/maintenance records,
operating manuals.
• Sample receipt and management practices.
• Analytical documentation, including any discrepancies and corrective actions.
• General procedures for data security, review, documentation, reporting and archiving.
• Data integrity issues such as proper manual integrations.
When the operations of a specific department are evaluated, a number of additional functions are
reviewed including:
• Detection limit studies
• Internal chain-of-custody documentation
• Documentation of standard preparations
• Quality Control limits and Control charts
Certain projects may require an internal audit to ensure laboratory conformance to site work plans,
sampling and analysis plans, QAPPs, etc.
A representative number of data audits are completed annually. The report format of any
discrepancy is similar to that of other internal audits.
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The laboratory, as part of their overall internal audit program, ensures that a review is conducted
with respect to any evidence of inappropriate actions or vulnerabilities related to data integrity.
Discovery of potential issues are handled in a confidential manner until such time as a follow up
evaluation, full investigation, or other appropriate actions are completed and the issues clarified.
All investigations that result in finding of inappropriate activity are documented and include any
disciplinary actions involved, corrective actions taken, and all appropriate notifications of
customers.
8.1.3 Internal Audit Reports and Corrective Action Plans
Additional information can be found in SOP S-ALL-Q-011 Audits and Inspections.
A full description of the audit, including the identification of the operation audited, the date(s) on
which the audit was conducted, the specific systems examined, and the observations noted are
summarized in an internal audit report. Although other personnel may assist with the performance
of the audit, the Quality Manager writes and issues the internal audit report identifying which audit
observations are deficiencies that require corrective action.
When audit findings cast doubt on the effectiveness of the operations or on the correctness of
validity of the laboratory's environmental test results, the laboratory will take timely corrective
action and notify the client in writing within 3 business days, if investigations show that the
laboratory results may have been affected.
Once completed, the internal audit report is issued jointly to the Laboratory General Manager and
the manager(s)/supervisor(s) of the audited operation at a minimum. The responsible
manager(s)/supervisor(s) responds within 14 days with a proposed plan to correct all of the
deficiencies cited in the audit report. The Quality Manager may grant additional time for responses
to large or complex deficiencies (not to exceed 30 days). Each response must include timetables for
completion of all proposed corrective actions.
The Quality Manager reviews the audit responses. If the response is accepted, the Quality Manager
uses the action plan and timetable as a guideline for verifying completion of the corrective action(s).
If the Quality Manager determines that the audit response does not adequately address the
correction of cited deficiencies, the response will be returned for modification.
To complete the audit process, the Quality Manager performs a re-examination of the areas where
deficiencies were found to verify that all proposed corrective actions have been implemented. An
audit deficiency is considered closed once implementation of the necessary corrective action has
been verified. If corrective action cannot be verified, the associated deficiency remains open until
that action is completed.
8.2 External Audits
PASI laboratories are audited regularly by regulatory agencies to maintain laboratory certifications, and by
customers to maintain appropriate specific protocols.
Audit teams external to the company review the laboratory to assess the existence of systems and degree of
technical expertise. The Quality Manager and other QA staff host the audit team and assist in facilitation of
the audit process. Generally, the auditors will prepare a formalized audit report listing deficiencies observed
and follow-up requirements for the laboratory. In some cases, items of concern are discussed during a
debriefing convened at the end of the on-site review process.
The laboratory staff and supervisors develop corrective action plans to address any deficiencies with the
guidance of the Quality Manager. The Laboratory General Manager provides the necessary resources for
staff to develop and implement the corrective action plans. The Quality Manager collates this information
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and provides a written report to the audit team. The report contains the corrective action plan and expected
completion dates for each element of the plan. The Quality Manager follows-up with the laboratory staff to
ensure corrective actions are implemented.
8.3 Quarterly Quality Reports
The Quality Manager is responsible for preparing a quarterly report to management summarizing the
effectiveness of the laboratory Quality Systems. This status report will include:
• Results of internal systems or performance audits
• Corrective action activities
• Discussion of QA issues raised by customers
• Results of third party or external audits
• Status of laboratory certifications
• Proficiency Testing Study Results
• Results of internal laboratory review activities
• Summary of holding time violations
• Method detection limit study status
• Training activity summary
• SOP revision summary
• 3P Implementation summary (internal program)
• Other significant Quality System items
The Corporate Director of Quality, Safety & Technology utilizes the information from each laboratory to
make decisions impacting the Quality Systems of the company as a whole. Each General Manager utilizes
the quarterly report information to make decisions impacting Quality Systems and operational systems at a
local level.
Additional information can be found in SOP S-ALL-Q-014 Quality System Review or its equivalent
revision or replacement.
8.4 Annual Managerial Review
A managerial review of Quality Systems is performed on an annual basis at a minimum. This allows for
assessing program effectiveness and introducing changes and/or improvements.
The managerial review must include the following topics of discussion:
• Policy and procedure suitability
• Manager/Supervisor reports
• Internal audit results
• Corrective and preventative actions
• External assessment results
• Proficiency testing studies
• Sample capacity and scope of work changes
• Client feedback, including complaints
This managerial review must be documented for future reference by the Quality Manager and copies of
the report are distributed to laboratory staff. The laboratory shall ensure that any actions identified during
the review are carried out within an appropriate and agreed timescale.
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9.0 CORRECTIVE ACTION
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During the process of sample handling, preparation and analysis, certain occurrences may warrant the necessity of
corrective actions. These occurrences may take the form of analyst errors, deficiencies in quality control, method
deviations, or other unusual circumstances. The Quality System of PASI provides systematic procedures for
documentation, monitoring and completion of corrective actions. This can be done using Pace's LabTrack system
that lists among other things, the deficiency by issue number, the deficiency source, responsible parry, root cause,
resolution, due date, and date resolved.
9.1 Corrective Action Documentation
The following items are examples of laboratory deviations or non-conformances that warrant some form of
documented corrective action:
• Quality Control data outside of acceptance criteria
• Sample Acceptance Policy deviations
• Missed holding times
• Instrument failures (including calibration failure)
• Sample preparation or analysis errors
• Sample contamination
• Errors in client reports
• Audit findings (internal and external)
• Proficiency Testing (PT) sample failures
• Client complaints or inquiries
Documentation of corrective actions may be in the form of a comment or footnote on the final report that
explains the deficiency (e.g. matrix spike recoveries outside of acceptance criteria) or it may be a more
formal documentation (either paper system or computerized spreadsheet). This depends on the extent of the
deficiency, the impact on the data, and the method or client requirements for documentation.
The person who discovers the deficiency or non-conformance initiates the corrective action documentation
on the Non-Conformance Corrective/ Preventative Action report and/or LabTrack. The documentation must
include the affected projects and sample numbers, the name of the applicable Project Manager, the client
name and the sample matrix involved. The person initiating the corrective action documentation must also
list the known causes of the deficiency or non-conformance as well as any corrective/preventative actions
that they have taken. Preventive actions must be taken in order to prevent or minimize the occurrence of the
situation.
In the event that the laboratory is unable to determine the cause, laboratory personnel and management staff
will start a root cause analysis by going through an investigative process. During this process, the following
general steps must be taken into account: defining the non-conformance problem, assigning responsibilities,
determining if the condition is significant, and investigating the root cause of the nonconformance problem.
General non-conformance investigative techniques follow the path of the sample through the process looking
at each individual step in detail. The root cause must be documented within LabTrack or on the
Corrective/Preventative Action Report.
After all the documentation is completed, the routing of the Corrective/Preventative Action Report and /or
LabTrack will continue from the person initiating the corrective action, to their immediate supervisor or the
Project Manager and finally to the Quality Manager, who is responsible for final review and signoff of all
formal corrective/preventative actions.
9.2 Corrective Action Completion
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9.2.1 Quality Control outside of acceptance criteria
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The analyst that is generating or validating Analytical data is responsible for checking the results
against established acceptance criteria (quality control limits). The analyst must immediately address
any deficiencies discovered. Method blank, LCS or matrix spike failures are evaluated against
method, program, and client requirements and appropriate footnotes are entered into the LIMS
system. Some deficiencies may be caused by matrix interferences. Where possible, matrix
interferences are confirmed by re-analysis.
Quality control deficiencies must be made known to the client on the final report for their review of
the data for usability. If appropriate, the supervisor is alerted to the QC failure and if necessary a
formal corrective action can be initiated. This may involve the input of the Quality Manager or the
General Manager.
The department supervisor and/or Operations Manager are responsible for evaluating the source of
the deficiency and for returning the analytical system to control. This may involve instrument
maintenance, analytical standard or reagent evaluation, or an internal audit of the analytical
procedure.
See applicable analytical SOPS for further guidance on QC acceptance criteria.
9.2.2 Sample Acceptance Policy deviations
Any deviation from the Sample Acceptance Policy listed in this Manual must be documented on the
Chain-of-Custody or other applicable form by the sample receiving personnel or by the Project
Manager. Analysts or supervisors that discover such deviations must contact the sample receiving
personnel or appropriate Project Manager so they can initiate the proper documentation and client
contact. If a more formalized corrective action must be documented, the Quality Manager is made
aware of the situation.
The client is notified of these deviations as soon as possible so they can make decisions on whether
to continue with the sample analysis or re-sample. Copies of this documentation are included in the
project file.
9.2.3 Missed holding times
In the event that a holding time requirement has been missed, the analyst or supervisor must
complete a formal corrective action form. The Project Manager and the Quality Manager must be
made aware of these hold time exceedances.
The Project Manager must contact the client for appropriate decisions to be made with the resolution
documented and included in the client project file. The Quality Manager includes a list of all missed
holding times in their Quarterly Report to the corporate office.
9.2.4 Instrument Failures
In the event of an instrument failure that either causes the necessity for re-analysis or questions the
validity of generated results, a formal corrective action must be initiated. The analyst and supervisor
evaluate any completed data for validity and usability. They are also responsible for returning the
instrument to valid operating condition and for documenting that the system is in control (e.g.
acceptable calibration verification).
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9.2.5 Sample Preparation or Analysis errors
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When there is an error in the preparation or analysis of samples, the analyst evaluates the impact on
the usability of the analytical data with the assistance of the supervisor or manager. The affected
samples will be re-processed or re-analyzed under acceptable conditions. In the event that no
additional sample is available for re-analysis, the client must be contacted for their decision on how
to proceed. Documentation may take the form of footnotes or a formal corrective action form.
9.2.6 Errors in client reports
When an error on the client report is discovered, the Project Manager is responsible for initiating a
formal corrective action form that describes the failure (e.g. incorrect analysis reported, reporting
units are incorrect, reporting limits do not meet objectives). The Project Manager is also responsible
for revising the final report if necessary and submitting it to the client.
9.2.7 Audit findings
The Quality Manager is responsible for documenting all audit findings and their corrective actions.
This documentation must include the initial finding, the persons responsible for the corrective action,
the due date for reporting back to the auditing body, the root cause of the issue, and the corrective
action taken to resolve the findings. The Quality Manager is also responsible for providing any
back-up documentation used to prove that a corrective action has been completed.
9.2.8 Proficiency Testing failures
Any PT result returned to the Quality Manager as "not acceptable" requires an investigation and
applicable corrective actions. The operational staff is made aware of the PT failures and they are
responsible for reviewing the applicable raw data and calibrations and list possible causes for error.
The Quality Manager reviews their findings and initiates another external PT sample or an internal
PT sample to try and correct the previous failure. Replacement PT results must be monitored by the
Quality Manager and reported to the applicable regulatory authorities.
9.2.9 Client Complaints
Project Managers are responsible for issuing corrective action forms for client complaints. As with
other corrective actions, the possible causes of the problem are listed and the form is passed to the
appropriate analyst or supervisor. After the corrective actions have been listed, the Project Manager
reviews the corrective action to determine if the client needs or concerns are being addressed.
Additional information can be found in SOP S-ALL-Q-012 Corrective Action/Preventative
Action Process.
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10.0 GLOSSARY
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3P Program The Pace Analytical continuous improvement program that focuses on Process,
Productivity and Performance. Best Practices are identified that can be used by all
PASI labs.
Accuracy The agreement between an observed value and an accepted reference value. Accuracy
includes a combination of random error (precision) and systematic error (bias)
components that are due to sampling and analytical operations; a data quality indicator.
Aliquot A portion of a sample taken for analysis.
Analyte The specific chemical species or parameter an analysis seeks to determine.
Batch Environmental samples that are prepared and/or analyzed together with the same
process and personnel, using the same lot(s) of reagents. A preparation batch is
composed of one to 20 environmental samples of the same NELAC-defined matrix,
meeting the above-mentioned criteria and with a maximum time between the start of
processing of the first and last sample in the batch to be 24 hours. An analytical batch
is composed of prepared environmental samples (extracts, digestates or concentrates)
that are analyzed together as a group. An analytical batch can include prepared
samples originating from various environmental matrices and can exceed 20 samples.
Blank A sample that has not been exposed to the analyzed sample stream in order to monitor
contamination during sampling, transport, storage or analysis. The blank is subjected
to the usual analytical and measurement process to establish a zero baseline or
background value and is sometimes used to adjust or correct routine analytical results.
Blind Sample A sample for submitted for analysis with a composition known to the submitter. The
analyst/laboratory may know the identity of the sample but not its composition. It is
used to test analyst or laboratory proficiency in the execution of the measurement
process.
Calibration To determine, by measurement or comparison with a standard, the correct value of
each scale reading on a meter, instrument, or other device. The levels of the applied
calibration standard must bracket the range of planned or expected sample
measurements.
Calibration Curve The graphic representation of known values, such as concentrations for a series of
calibration standards and their instrument response.
Chain-of-Custody A record that documents the possession of samples from the time of collection to
(COC) receipt in the laboratory. This record generally includes the number and type of
containers, mode of collection, collector, time of collection, preservation, and
requested analyses.
Confirmation Verification of the identity of a component through the use of an alternate scientific
approach from the original method. These may include, but are not limited to:
• second-column confirmation
• alternate wavelength
• derivatization derivative
• mass spectral interpretation
• additional cleanup procedures
Contract Required Detection limit that is required for EPA Contract Laboratory Program (CLP) contracts.
Detection Limit (CRDL)
Contract Required Quantitation limit (reporting limit) that is required for EPA Contract Laboratory
Quantitation Limit Program (CLP) contracts.
(CRQL)
Comparability An assessment of the confidence with which one data set can be compared to another.
Comparable data are produced through the use of standardized procedures and
techniques.
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Completeness The percent of valid data obtained from a measurement system compared to the
amount of valid data expected under normal conditions. The equation for
completeness is:
% Completeness = (Valid Data Points/Expected Data Points)* 100
Calibration Verification The process of verifying a calibration by analysis of standards and comparing the
results with the known amount.
Control Chart A graphic representation of a series of test results, together with limits within which
results are expected when the system is in a state of statistical control (see definition
for Control Limit)
Control Limit A range within which specified measurement results must fall to verify that the
analytical system is in control. Control limit exceedances may require corrective
action or require investigation and flagging of nonconforming data.
Corrective Action The action taken to eliminate the causes of a nonconformity, defect, or other
undesirable situation in order to prevent recurrence.
Corrective and The primary management tools for bringing improvements to the quality system, to
Preventative Action the management of the quality system's collective processes, and to the products or
(CAPA) services delivered which are an output of established systems and processes.
Data Quality Objective Systematic strategic planning tool based on the scientific method that identifies and
(DOQ) defines the type, quality, and quantity of data needed to satisfy a specified use or end
user.
Data Reduction The process of transforming raw data by arithmetic or statistical calculations, standard
curves, concentration factors, etc., and collation into a more usable form.
Demonstration of A procedure to establish the ability of the analyst to generate acceptable accuracy.
Capability
Detection Limit (DL) General term for the lowest concentration or amount of the target analyte that can be
identified, measured and reported with confidence that the analyte concentration is not
a false positive value. See definitions for Method Detection Limit and Limit of
Detection.
Document Control Procedures to ensure that documents (and revisions thereto) are proposed, reviewed for
(Management) accuracy, approved for release by authorized personnel, distributed properly and
controlled (managed) to ensure use of the correct version at the location where the
prescribed activity is performed.
Dry Weight The weight after drying in an oven at a specified temperature.
Duplicate or Replicate The identically performed measurement on two or more sub-samples of the same
Analysis sample within a short interval of time
Environmental Sample A representative sample of any material (aqueous, non-aqueous, or multimedia)
collected from any source for which determination of composition or contamination is
requested or required. Environmental samples can generally be classified as follows:
• Non Potable Water ( Includes surface water, ground water, effluents, water
treatment chemicals, and TCLP leachates or other extracts)
• Drinking Water - Delivered (treated or untreated) water designated as potable
water
• Water/Wastewater - Raw source waters for public drinking water supplies,
ground waters, municipal influents/effluents, and industrial influents/effluents
• Sludge - Municipal sludges and industrial sludges.
• Soil - Predominately inorganic matter ranging in classification from sands to
clays.
• Waste - Aqueous and non-aqueous liquid wastes, chemical solids, and
industrial liquid and solid wastes
Equipment Blank A sample of analyte-free media used to rinse common sampling equipment to check
effectiveness of decontamination procedures.
Field Blank A blank sample prepared in the field by filling a clean container with reagent water and
appropriate preservative, if any, for the specific sampling activity being undertaken.
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Field Measurement Determination of physical, biological, or radiological properties, or chemical
constituents that are measured on-site, close in time and space to the matrices being
sampled/measured, following accepted test methods. This testing is performed in the
field outside of a fixed-laboratory or outside of an enclosed structure that meets the
requirements of a mobile laboratory.
Holding Time The maximum time that samples may be held prior to preparation and/or analysis as
defined by the method.
Homogeneity The degree to which a property or substance is uniformly distributed throughout a
sample.
Initial Calibration The process of analyzing standards, prepared at specified concentrations, to define the
(ICAL) quantitative response relationship of the instrument to the analytes of interest Initial
calibration is performed whenever the results of a calibration verification standard do
not conform to the requirements of the method in use or at a frequency specified in the
method.
ILT Instructor Led Training
Internal Standards A known amount of standard added to a test portion of a sample as a reference for
evaluating and controlling the precision and bias of the applied analytical method.
Intermediate Standard Reference solutions prepared by dilution of the stock solutions with an appropriate
Solution solvent.
Laboratory Control A blank sample matrix, free from the analytes of interest, spiked with known amounts
Sample (LCS) of analytes or a material containing known amounts of analytes. It is generally used to
establish intra-laboratory or analyst-specific precision and bias or to assess the
performance of all or a portion of the measurement system. Sometimes referred to as
Laboratory Fortified Blank, Spiked Blank or QC Check Sample.
Limit of Detection An estimate of the minimum amount of a substance that an analytical process can
(LOD) reliably detect An LOD is analyte and matrix specific and may be laboratory-
dependent.
Limit of Quantitation The minimum levels, concentrations or quantities of a target variable (e.g. target
(LOQ) . analyte) that can be reported with a specified degree of confidence
Laboratory Information A computer system that is used to maintain all sample information from sample
Management System receipt, through preparation and analysis and including sample report generation.
(LIMS)
LMS Learning Management System
Lot A quantity of bulk material of similar composition processed or manufactured at the
same time.
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Matrix The component or substrate that contains the analyte of interest. For purposes of batch
and QC requirement determinations, the following matrix distinctions are used:
• Aqueous or Non-Potable Water: any aqueous sample excluded from the
definition of Drinking Water matrix or Saline/Estuarine source. Includes
surface water, groundwater, effluents, and TCLP or other extracts.
• Drinking Water: any aqueous sample that has been designated a potable or
potentially potable water source.
• Saline/Estuarine: any aqueous sample from an ocean or estuary, or other
saltwater source.
• Non-aqueous liquid: any organic liquid with <15% settleable solids.
• Biological Tissue: any sample of a biological origin such as fish tissue,
shellfish or plant material. Such sample can be grouped according to origin.
• Solid: includes soils, sediments, sludges, and other matrices with >15%
settleable solids.
• Chemical Waste: a product or by-product or an industrial process that
results in a matrix not previously defined
• Air and Emissions: whole gas or vapor samples including those contained
in flexible or rigid wall containers and the extracted concentrated analytes of
interest from a gas vapor that are collected with a sorbent tube, impinger
solution, filter, or other device.
Matrix Spike (MS) A sample prepared by adding a known quantity of target analyte to a specified amount
of matrix sample for which an independent estimate of target analyte concentration is
available. Matrix spikes are used to determine the effect of the matrix on a method's
recovery efficiency. (sometimes referred to as Spiked Sample or Fortified Sample)
Matrix Spike Duplicate A second replicate matrix spike prepared in the laboratory and analyzed to obtain a
(MSD) measure of precision of the recovery of each analyte. (sometimes referred to as Spiked
Sam le Du licate or Fortified Sample Duplicate)
Method Blank A sample of a matrix similar to the batch of associated samples (when available) that is
free from the analytes of interest and is processed simultaneously with and under the
same conditions as samples through all steps of the analytical procedures: and in which
no target analytes or interferences are present at concentrations that impact the
analytical results for sample analyses.
Method Detection Limit One way to establish a Limit of Detection (LOD); defined as the minimum
(MDL) concentration of a substance that can be measured and reported with 99% confidence
that the analyte concentration is greater than zero and is determined from analysis of a
sample in a given matrix containing the analyte.
Performance Based An analytical system wherein the data quality needs, mandates or limitations of a
Measurement System program or project are specified and serve as criteria for selecting appropriate test
(DBMS) methods to meet those needs in a cost-effective manner.
Precision The degree to which a set of observations or measurements of the same property,
obtained under similar conditions, conform to themselves. Precision is usually
expressed as standard deviation, variance or range, in either absolute or relative terms.
Preservation Refrigeration and/or reagents added at the time of sample collection (or later) to
maintain the chemical and/or biological integrity of the sample.
Proficiency Testing A means of evaluating a laboratory's performance under controlled conditions relative
to a given set of criteria through analysis of unknown samples provided by an external
source.
Protocol A detailed written procedure for field and/or laboratory operation that must be strictly
followed.
Quality Assurance A formal document describing the detailed quality control procedures required by a
Project Plan (QAPP) specific project.
Quality Assurance (QA) An integrated system of activities involving planning, quality control, quality
assessment, reporting and quality improvement to ensure that a product or service
meets defined standards of quality with a stated level of confidence.
GLOSSARY
eAnalytical
Quality Assurance Manual
Revision: 11.0
Page 49 of 73
Quality Control (QC) The overall system of technical activities whose purpose is to measure and control the
quality of a product or service so that it meets the needs of users.
Quality Control Sample A sample used to assess the performance of all or a portion of the measurement
system. QC samples may be Certified Reference Materials, a quality system matrix
fortified b s ikin , or actual samples fortified b spiking.
Quality Assurance A document stating the management policies, objectives, principles, organizational
Manual structure and authority, responsibilities, accountability, and implementation of an
agency, organization, or laboratory, to ensure the quality of its product and the utility
of its product to its users.
Quality System A structured and documented management system describing the policies, objectives,
principles, organizational authority, responsibilities, accountability, and
implementation plan of an organization for ensuring quality in its work processes,
products (items), and services. The quality system provides the framework for
planning, implementing, and assessing work performed by the organization and for
carrying out required QA and QC.
Random Error The EPA has established that there is a 5% probability that the results obtained for any
one analyte will exceed the control limits established for the test due to random error.
As the number of compounds measured increases in a given sample, the probability for
statistical error also increases.
Raw Data Any original factual information from a measurement activity or study recorded in a
laboratory notebook, worksheets, records, memoranda, notes, or exact copies thereof
that are necessary for the reconstruction and evaluation of the report of the activity or
study. Raw data may include photography, microfilm or microfiche copies, computer
printouts, magnetic media, including dictated observations, and recorded data from
automated instruments. If exact copies of raw data have been prepared (e.g. tapes
which have been transcribed verbatim, dated and verified accurate by signature), the
exact copy or exact transcript may be submitted.
Reagent Grade Analytical reagent (AR) grade, ACS reagent grade, and reagent grade are synonymous
terms for reagents that conform to the current specifications of the Committee on
Analytical Reagents of the American Chemical Society.
Reference Standard A standard, generally of the highest metrological quality available at a given location,
from which measurements made at that location are derived.
Reporting Limit (RL) The level at which method, permit, regulatory and client specific objectives are met.
The reporting limit may never be lower than the Limit of Detection (i.e. statistically
determined MDL). Reporting limits are corrected for sample amounts, including the
dry weight of solids, unless otherwise specified. There must be a sufficient buffer
between the Reporting Limit and the MDL.
Representativeness A quality element related to the ability to collect a sample reflecting the characteristics
of the part of the environment to be assessed. Sample representativeness is dependent
on the sampling techniques specified in the project work plan.
Sample Delivery Group A unit within a single project that is used to identify a group of samples for delivery.
(SDG) An SDG is a group of 20 or fewer field samples within a project, received over a
period of up to 14 calendar days. Data from all samples in an SDG are reported
concurrently.
Sample Tracking Procedures employed to record the possession of the samples from the time of
sampling until analysis, reporting and archiving. These procedures include the use of a
Chain-of-Custody Form that documents the collection, transport, and receipt of
compliance samples to the laboratory. In addition, access to the laboratory is limited
and controlled to protect the integrity of the samples.
Sensitivity The capability of a method or instrument to discriminate between measurement
responses representing different levels (concentrations) of a variable of interest
Standard A substance or material with properties known with sufficient accuracy to permit its
use to evaluate the same property in a sample.
GLOSSARY
eAnalytical
Quality Assurance Manual
Revision: 11.0
Page 50 of 73
Standard Blank A calibration standard consisting of the same solvent/reagent matrix used to prepare
the calibration standards without the analytes. It is used to construct the calibration
curveb establishin instrument background.
Standard Operating A written document which details the method of an operation, analysis, or action
Procedure (SOP) whose techniques and procedures are thoroughly prescribed and which is accepted as
the method for performing certain routine or repetitive tasks
Stock Standard A concentrated reference solution containing one or more analytes prepared in the
laboratory using an assayed reference compound or purchased from a reputable
commercial source.
Surrogate A substance with properties that mimic the analyte of interest It is unlikely to be
found in environmental samples and is added to them for quality control purposes.
Systems Audit An on-site inspection or assessment of a laboratory's quality system.
Traceability The property of a material or measurement result defining its relationship to
recognized international or national standards through an unbroken chain of
comparisons.
Training Document A training resource that provides detailed instructions to execute a specific method or
job function.
Trip Blank This blank sample is used to detect sample contamination from the container and
preservative during transport and storage of the sample. A cleaned sample container is
filled with laboratory reagent water and the blank is stored, shipped, and analyzed with
its associated samples.
Uncertainty The parameter associated with the result of a measurement that characterized the
Measurement dispersion of the values that could be reasonably attributed to the measurand ( i.e. the
concentration of an analyte).
WBT Web based training
GLOSSARY
Quality Assurance Manual
aceI'l ,1'?nal y}ica f Revision: 11.0
y c I Page 51 of 73
11.0 REFERENCES
• "Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act." Federal
Register, 40 CFR Part 136.
• "Test Methods for Evaluating Solid Wastes: Physical/Chemical Methods." SW-846.
• "Methods for Chemical Analysis of Water and Wastes", EPA 600-4-79-020, 1979 Revised 1983, U.S. EPA.
• U. S. EPA Contract Laboratory Program Statement of Work for Organic Analysis
• U. S. EPA Contract Laboratory Program Statement of Work for Inorganic Analysis
• "Standard Methods for the Examination of Water and Wastewater." Current Edition APHA-AWWA-WPCF
• "Annual Book of ASTM Standards", Section 4: Construction, Volume 04.04: Soil and Rock; Building Stones,
American Society of Testing and Materials.
• "Annual Book of ASTM Standards", Section 11: Water and Environmental Technology, American Society of
Testing and Materials.
• "NIOSH Manual of Analytical Methods", Third Edition, 1984, U.S. Department of Health and Human
Services, National Institute for Occupational Safety and Health.
• "Methods for the Determination of Organic Compounds in Finished Drinking Water and Raw Source Water'
U. S. EPA, Environmental Monitoring and Support Laboratory - Cincinnati (September 1986).
• Quality Assurance of Chemical Measurements, Taylor, John K.; Lewis Publishers, Inc. 1987
• Methods for Non-conventional Pesticides Chemicals Analysis of Industrial and Municipal Wastewater, Test
Methods, EPA-440/1-83/079C
• Environmental Measurements Laboratory (EML) Procedures Manual, HASL-300, US DOE, February, 1992.
• Requirements for Quality Control of Analytical Data, HAZWRAP, DOE/HWP-65/R I, July, 1990.
• Requirements for Quality Control of Analytical Data for the Environmental Restoration Program, Martin
Marietta, ES/ER/TM-16, December, 1992.
• Quality Assurance Manual for Industrial Hygiene Chemistry, AIHA, 1988
• National Environmental Laboratory Accreditation Conference, Constitution, Bylaws, and Standards. Most
recent
• ISO/IEC 17025:2005, General requirements for the competence of testing and calibration laboratories.
REFERENCES
Quality Assurance Manual
'l, nal tica J Revision: 11.0
1'!;a'ce Analytical`
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12.0 REVISIONS
The PASI Corporate Quality and Safety Manager files both a paper copy and electronic version of a Microsoft
Word document with tracked changes detailing all revisions made to the previous version of the Quality Assurance
Manual. This document is available upon request. All revisions are summarized in the table below.
Document Number Reason for Change Date
Quality Assurance Overall conversion to template format Removed all references to Addenda. September 17',
Manual Revision 11.0 Changes required based on conversion are not explicitly noted unless change 2007
represents a significant policy change.
SECTION 1:
Add comment to address continuous improvement to quality system.
Changed statement of purpose in Section header to "Mission Statement".
Added requirements for appointment when Technical Director absent.
Added requirements for notification to AA's and updates to
organizational charts when management changes.
Added Client Services Manager job description.
SECTION 2:
Changed temperature requirements to "Not Frozen but <6°C".
Added flexible section concerning default sampling time in absence of
client specified time.
Added flexible section to address sample and container identification by
the LIMS.
Changed sample retention requirement to 45 days from receipt of
samples. Added comment allowing for storage outside of temperature
controlled conditions.
SECTION 3:
Inserted allowance for use of older methods.
Changed references to work processing and training documents to allow
for use of LMS and other types of training media.
Inserted allowance for alternative DOCs where spiking not possible.
SECTION 4:
Inserted reference to Anonymous Message line.
Inserted reference to the use of default control limits.
Inserted allowance for release of data without corrective action for
obvious matrix interferences.
Inserted reference to the treatment of internal standards.
Inserted allowance for use of MDL annual MDL verification in lieu of
full 40 CFR Part 136 annual MDL studies.
Inserted general procedure for LOQ verification
SECTION 5:
Added general process for approval and use of QAM template.
Removed specific reference of Work Process Manuals. Left flexible
section to include all other controlled documentation.
SECTION 6:
No changes noted.
SECTION 7:
Added qualifications for secondary reviewers.
SECTION 8:
Changed frequency listing for Corporate Audits.
SECTION 9:
Changed references from QA Track to Lab Track - left flexible to
REVISIONS
eAnalytical
Quality Assurance Manual
Revision: 11.0
Page 53 of 73
Document Number Reason for Change Date
accommodate information still in QA Track.
SECTION 10:
No changes noted.
SECTION 11:
No changes noted.
ATTACHMENTS:
Standardized format for Attachments.
Quality Assurance Throughout the document, Pace was replaced with PASI or in some cases June 20th, 2006
Manual Revision 10.0 with Pace Analytical. Also, corrections were made to wording, grammar,
spelling, and formatting.
SECTION 1:
Updated the PASI mission statement
Deleted Financial Responsibility, Drug-Free Workplace, Non-
Harassment, Proper and Professional Conduct, Protection of Property,
and Communication sections.
Added Assistant General Manager/ Operations Manager, Technical
Director, Administrative Business Manager, Project Manager, Project
Coordinator, Field Analyst, Laboratory Technician & Field Technician
job descriptions
Added detailed Chain of Command to Laboratory Organization section
Updated the Training and Orientation section to reflect current practices
Deleted a portion of the Laboratory Safety section and added a reference
to the Safety Manual and Chemical Hygiene Plan.
SECTION 2:
Switched the order of Chain of Custody and Sample Acceptance Policy
sections
Added details of project review documentation to Project Initiation
section
Added steps to sample log in
SECTION 3:
Deleted reference to local addenda for company wide SOPS
Rearranged sentences
Added "PASI will not be liable if the client chooses not to follow PASI
recommendations" to the Regulatory and Method Compliance section.
SECTION 4:
Added details to the documentation of review or investigation of possible
data integrity.
Corrected wording in Method Blank section
Deleted from LCS/LCSD section an out-of-control statement that said
affected samples associated with a failing LCS must be re-analyzed
SECTION 5:
Added "Electronic documents must be readily accessible to all facility
employees" to Documents Management section
Updated the Standard Operating Procedure section to describe the new
PASI corporate SOP Templates and distribution.
SECTION 6:
Re-organized & re-named sections
Updated the interpretation of the Calibration Verification policy
Added clarification to the definition of the Second Source Standard
Revised Single Point Calibration procedure to address NELAC
requirement
REVISIONS
eAnalytical
Quality Assurance Manual
Revision: 11.0
Page 54 of 73
Document Number Reason for Change Date
Incorporated Spare Parts into Instrument/ Equipment Maintenance
SECTION 7:
Updated Analytical Results Processing section to clarify data
documentation policy.
Deleted "All data that are manually entered into the LIMS is reviewd at a
rate of 100%" and deleted the use of checklists statement from Data
Verification section
Integrated paragraphs for better flow
Deleted item # 15, "If required, a statement of the estimated uncertainty
of the test results." from the Data Reporting section
Added Data Security section to describe PASI data security practices
Added fire, flood, and vermin protection requirement to Data Archiving
section
Added statement to Data Archiving section describing that NELAP
related records are available to accrediting authorities.
Added Data Disposal section
SECTION 8:
Deleted first paragraph stating that Pace labs are subject to internal and
external audits and reviews.
Added description of PASI internal audit program and investigations
Added requirement that corrective action be taken and client notified
within 3 days if audit findings show that test results may have been
affected
Updated requirement for manager(s)/supervisor(s) to respond to audit
findings with a plan to correct all deficiencies within 14 days. Statement
included that allows Quality Manager to grant additional time for
response.
Added to Annual Managerial Review section that "The laboratory shall
ensure that any actions identified during the review are carried out within
an appropriate and agreed timescale."
SECTION 9:
Added documentation requirement for reporting discovery of deficiency
or non-conformance, must be documented "on the Non-Conformance
Corrective/ Preventative Action report and/or QA Trak."
Added "Preventative actions must be taken in order to prevent or
minimize the occurrence of the situation."
Added a paragraph to describe the new PASI Root Cause Analysis
procedure.
SECTION 10:
Added the following definitions: Contract Required Detection Limit
(CRDL), Contract Required Quantitation Limit (CRQL), Corrective and
Preventative Action (CAPA), Non Potable Water (to Environmental
Sample definition), Intermediate Standard Solution, Quality Control
Sample, Stock Standard, Uncertainty Measurement, Working Standard
Solution,
SECTION 11:
Added ISO/IEC 17025:2005 reference
Appendix:
Added Appendix L Quality Control Calculations
REVISIONS
eAnalytical
ATTACHMENT I
Quality Control Calculations
PERCENT RECOVERY (%REC)
%REC = (MSConc - SampleConc) * 100
True Value
NOTE: The SampleConc is zero (0) for theLCS and Surrogate Calculations
PERCENT DIFFERENCE (%D)
%D - MeasuredValue - True Value *100
True Value
Quality Assurance Manual
Revision: 11.0
Page 55 of 73
where:
TrueValue = Amount spiked (can also be the CF or RF of the ICAL Standards)
Measured Value = Amount measured (can also be the CF or RF of the CCV)
PERCENT DRIFT
CalculatedConcentration - TheoreticalConcentration
%Drift = * 100
TheoreticalConcentrtion
RELATIVE PERCENT DIFFERENCE (RPD)
(RI -R2)1
RPD = 100
(Rl+R2)/2
where:
RI = Result Sample 1
R2 = Result Sample 2
CORRELATION COEFFICIENT (R)
N
?W,.*(X,.-X)*(Y,.-T)
CorrCoeff =
C W,. * (X; -X)2 ? * C?W. * (Y,. -T )2?
With: N Number of standard samples involved in the calibration
i Index for standard samples
Wi Weight factor of the standard sample no. i
Xi X-value of the standard sample no. i
X(bar) Average value of all x-values
Yi Y-value of the standard sample no. i
Y(bar) Average value of all y-values
aceAnalytical?
ATTACHMENT I (CONTINUED)
Quality Control Calculations (continued)
STANDARD DEVIATION (S)
S (X, - x)2
"
=
(n -1)
where:
n = number of data points
X; = individual data point
x = average of all data points
AVERAGE(
i
Y xi
X= n=1
n
where:
n = number of data points
X; = individual data point
RELATIVE STANDARD DEVIATION (RSD)
RSD = S *100
X
where:
S = Standard Deviation of the data points
7 = average of all data points
Quality Assurance Manual
Revision: 11.0
Page 56 of 73
aceAnalytical?
ATTACHMENT IIA
Quality Assurance Manual
Revision: 11.0
Page 57 of 73
PASI - MINNESOTA ORGANIZATIONAL CHART
f 2aceAnalytical'
dive Business Manager General Manager
Jessica Lewis Sarah Cherney
Director of Quality, Safety & Training
Brad Meadows
Client Services Supervisor
CSS Aileen Van Bergen
Sample Receiving
CST2 Henry Fritchman
CST1 Matthew Iniguez
CST1 Cory Lund
CST1 Andy Pritchett
CST1 Joanne Richardson
CST1 Yeng Thao
Air Lab
LM Amy Peterson
Air - 1039
LA2 Heather Green
LT3 Bryan Rector
LA2 Laurel Weinkauf
Date
Sarah Cherney, General Manager
Last Revised: October 10, 2007
*Lead Analyst
**Safety Officer
Administrative Support
SC2 Michel Gabel
SC2 Emily Michels (T) I I Regional Sales Manager
Mike King
Client Services Manager Technical Sales Manager
Michelle Kruse TSM Chris Bremer
Air Technical Director
Project Management Project Coordinator pM3 Daryl Pete son
PM3 Diane Anderson PC Nate Habte
PM3 Carol Davy PC Sylvia Hunter
SAE M
Ch
i
ti
PM3 Norm Hoffa PC Allison Puckett ary
r
s
e
PM1 Paul Kirchberg PC Julie Thieschafer SAE Kan Hermansen
NAM Geoff Pellechia
PM1 Colin Schutt SAE J
ff S
ith
PM3 Carolynne Trout e
m
PM3 Scott Unze
Building Maintenance Lab Technical Manager
Courier BS Bob Wilkins LTM Brian Pike
CST1 Shawn Davis
Upper Midwest Region
Quality Assurance Manager II
Julie Trivedi
I Quality Assurance Manager I
Melanie Ollila**
SC2 Madolyn Elias
QAA Charity Nowlan
Organic Lab
Inorganic Lab
Dioxin Lab
LM Pam Olah
I LS3 Ed Kehoe
VOrganic Lab Semivolatile Organic Lab
Dan Tocko LS1 Adam Haugerud Metals -1020

GCMS -1034
GCMS -1030 LT3 Linda Brown
LA2 Tom Mellem Prep -1035
LT2 Carin Curtis LA2 Julie Brenner LT2 Irina Petrakova LT2 Diana Brusky

LT2 Mike Heckman
LT2 Anna Hallberg
LA2 Bob Schnobrich LT2
Peter emas
LA2 Janielle Ward LA1 Kristen Pierce LT2 Ken Hoelscher
LA3 Matt Hogenson
GC-1033 GCILC-1031 Wet Chem -1021
LA2 Nicole Herried LT1 Paul Huelsman-Voyer
LA2 Roberta Provost LA1 Nelima Kerre LT2 Jed Levitt LT2 Chris Reindl
LA1 Kelly Lightner * LT3 Noel Sigler*
LA1 Andrea Opland
LT3 Matthew Streit
Organic Prep -1032 Analytical -1035
LT2 Rachel Dugan LA1 Ayokosok Enow
LA1 Jessica Heinecke LA1 Brandon Gaylord
LA1 Jessica Johnson LA3 Steve Hannan
LT2 Laramie Roecker LA3 Barb Larka
LT3 Fong Thao LA3 Chuck Sueper
LT2 Meng Thao LA3 Sue Thorson
SM Dave White
Minnesota Laboratory
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Quality Assurance Manual
Revision: 11.0
Page 58 of 73
ATTACHMENT IIB
PASI - CORPORATE ORGANIZATIONAL CHART
Chief Fxecutive Officer
Administrative
Assistant
Director of
Training
General Manager
Lab Ops
General Manager
MNField
Chief Operations Vice President, Sales Director Quality, Chief Financial
Officer & Marketing Safety, Technology Officer
General Manager
Director of
North Carolina Labs Corporate Marketing Corporate Quality hiformation
Manager Manager Technology
General Manager
Green Bay Lab
Regional Sales
General Manager Managers
Indianapolis Lab

Director of Human
Resources
General Manager
Kansas Lab
Purchasing
General Manager
Mmn ota Lab
General Manager
New Orleans Lab
General Manager
Pennsylvania Labs
General Manager
Puerto Rico Lab
aceAnalytical?
ATTACHMENT III
PASI - MINNESOTA EQUIPMENT LIST
Quality Assurance Manual
Revision: 11.0
Page 59 of 73
MODEL
INSTRUMENT MANUFACTURER NUMBER DETECTORS ANALYSIS
GC/MS/VOA Hewlett-Packard 5890 PID/FID T03/AIR
GC/MS/VOA Agilent 6890/5973 MS T014/TO15
GC/MS/VOA Hewlett-Packard 5890/5972 MS T014/TO15
GC/MS/VOA Hewlett-Packard 6890 / 5973 MS SW8260
GC/MS/VOA Hewlett-Packard 6890 / 5973 MS SW8260
GC/MS/VOA Hewlett-Packard 6890 / 5973 MS SW8260
GC/MS/VOA Agilent 6890 / 5973 SW8260
GC/MS/VOA Hewlett-Packard 6890 / 5973 MS SW8260
GC/MS/VOA Agilent 6890/5973 MS 524.2
GC/MS/VOA Agilent 6890/5973 MS T014/TO15
GC/MS/SMVOA Hewlett-Packard 5890 / 5972 MS BNA

GC/MS/SMVOA Hewlett-Packard 6890/5973
MS SIM,agList,
cPAH
GC/MS/SMVOA Hewlett-Packard 5890 8270 SIM

GC/MS/SMVOA Agilent 6890/5973
MS SIM,agList,
cPAH
GC/MS/SMVOA Agilent 6890/5973 MS PCDD/PCDF
GC/MS/SMVOA Agilent 6890/5973 MS BNA
GC PETROLEUM
RELATED VOLATILES Hewlett-Packard 5890
PID/FID
BTEX
GC PETROLEUM
RELATED VOLATILES Hewlett-Packard 5890
PID/FID
BTEX
GC PETROLEUM
RELATED VOLATILES Hewlett-Packard 5890
PID/FID
T03/AIR
GC PETROLEUM
RELATED VOLATILES Agilent 6890/1888 TCD/FID
Headspace
GC PETROLEUM
RELATED VOLATILES Hewlett-Packard 5890 TCD/FID Fixed Gases
GC PETROLEUM
RELATED SMVOA Hewlett-Packard 5890 FID DRO
GC SMVOA Hewlett-Packard 5890 DUAL ECD PCB
GC SMVOA Hewlett-Packard 6890 DUAL ECD Pest/PCB
GC SMVOA Hewlett-Packard 6890 FID DRO
HPLC Hewlett-Packard 1100 Series UV/FL/MS PAH

ICP Perkin-Elmer Optima
3300DV SCCD Metals

ICP Perkin-Elmer Optima
4300DV SCCD Metals
ICP/MS Perkin-Elmer ELAN9000 MS Metals
MERCURY ANALYZER Perkin-Elmer FIMS 100 Spectrometer Mercury
2eAnalytical?
Quality Assurance Manual
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AUTO ANALYZER Konelab 20 Spectrometer Anions
ION CHROMATOGRAPH Dionex DX5000 Conductivity Anions
OVEN Tempcon N8620-10 NA Preparation
OVEN Lab Line Imperial II NA Preparation
OVEN Despatch NA NA AIR
OVEN VWR 1370F NA General
OVEN Precision STM135 NA General
OVEN Thelco 130DM NA General
OVEN Baxter DK63 NA HRMS
OVEN Fisher Scientific 650G NA % moisture
OVEN Fisher Scientific 550-126 NA General
INCUBATOR Fisher Scientific 307 NA BOD
INCUBATOR VWR 2020 NA BOD
TURBIDITY HF Scientific Micro 100 NA Turbidity
TURBIDITY HF Scientific Micro 100 NA Turbidity
AUTOCLAVE Heinicke Co. Sterilquick NA Autoclave
AUTOCLAVE Market Forge Sterilmatic NA Autoclave
CENTRIFUGE Becton Dickenson Compactll NA HRMS
HIGH RESOLUTION
MASS SPECTROMETER
MicroMass
Ultimas
MS
PCDD/PCDF
HIGH RESOLUTION
MASS SPECTROMETER
MicroMass
Ultimas
MS
PCDD/PCDF
HIGH RESOLUTION
MASS SPECTROMETER
VG
AUTOSPEC
MS
PCDD/PCDF
HIGH RESOLUTION
MASS SPECTROMETER
MicroMass
AUTOSPEC
MS
PCDD/PCDF
DISSOLVED OXYGEN
METER
YSI
5000
NA
BOD
ION ANALYZER Orion EA 940 NA pH
ION ANALYZER Orion EA 940 NA fluoride, pH
pH METER Orion 290A NA pH

CONDUCTIVITY METER
Oakton RS232/CON
110
Probe - 1 D7 specific
conductivity
COD REACTOR Bioscience NA COD
MICROWAVE
EXTRACTION UNIT
Milestone
Ethos E
NA
Dioxin

MIDI DISTILLATION UNIT
Env. Express
Pace # 19582 CN, NH3,
phenols

MIDI DISTILLATION UNIT
Env. Express
Pace # 19604 CN, NH3,
phenols
METALS MICROWAVE
DIGESTOR
CEM Corporation
MDS-2100
NA
Metals Dig
METALS HOT BLOCK Env. Express SC 154 NA Metals Dig
METALS HOT BLOCK Env. Express SC 154 NA Metals Dig
METALS HOT BLOCK Env. Express SC 154 NA Metals Dig
SONICATOR Misonix XL 2020 NA 3550
2eAnalytical?
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Revision: 11.0
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SONICATOR Misonix XL 2015 NA 3550
SONICATOR Misonix 3000 3550
SONICATOR Misonix 3000 3550

DENVER MAXX BALANCE Denver
Instrumentation
MXX-212
NA
NA
A&D BALANCE A&D FX 3200 Soil Prep
BALANCE A&D FX 4000 NA
BALANCE Mettler AJ100 NA
BALANCE A&D FX-3200 NA
MilliQ Purification System MilliQ MiIIiQUV plus NA
aceAnalytical?
ATTACHMENT IV
PASI - MINNESOTA
Quality Assurance Manual
Revision: 11.0
Page 62 of 73
aceAnalytical?
ATTACHMENT V
PASI - MINNESOTA SOP LIST
Quality Assurance Manual
Revision: 11.0
Page 63 of 73
SOP Title SOP Number
Determination of Methane, Ethane, and Ethene in Air Modified TO-3 S-MN-A-002
Analysis of Air Samples for Volatile Organic Compounds b Gas Chromato rah /PID-FID method TO-3 S-MN-A-003
Cleaning, Certification, Leak Checking and Preparation for Shipment of SUMMA Passivated Canisters S-MN-A-004
Determination of Fixed Gases in Air b Modified 3C S-MN-A-005
Methane, Ethane, Ethene, and Propane in Water by GCFID mod. 3810 and RSK 175 S-MN-A-007
Sample Preparation and Analysis of Polychlorinated Biphenyls (PCBs) in Ambient Air using High Volume
Polyurethane Foam
S-MN-A-010
Analysis of Whole Air Sample for Volatile Organic Compound by GC/MS EPA T015/TO14 S-MN-A-013
Analysis of Whole Air Sample for Volatile Organic Compound by GC/MS EPA T015-SIM S-MN-A-014
Operation and Maintenance of the Perkin Elmer ELAN 6000 ICP-MS S-MN-BE-004
Sample Management S-MN-C-001
Bottle Order Database S-All-C-002
Bottle Preparatation S-MN-C-003
Internal Chain of Custody S-MN-C-005
Subcontracting Samples S-MN-C-004
Preparing Waste for Shipment S-MN-C-703
Preparation and Analysis of Samples for the Determination of Dioxins and Furans by USEPA Method
8290
S-M N-H-001
Preparation and Analysis of Samples for the Determination of Dioxins and Furans using USEPA Method
1613B
S-M N-H-002
Preparation and Analysis of Samples for the Determination of 2,3,7,8-TCDD using USEPA Method
1613B, Drinking Water
S-MN-H-003
Percent Lipids Determination S-MN-H-004
Preparation and Analysis of Samples for the Determination of PCDDs, PCDFs, and PCBs by modified
USEPA Method 23, T09, or NY State Guidelines
S-MN-H-005
Preparation and Analysis of Samples for the Determination of Dioxins and Furans by USEPA Method
8280
S-M N-H-007
Method 1668, PCB Congenger (WHO List) S-MN-H-009
Method 1653, Chorinated Phenols S-MN-H-010
Preparation and Analysis of Samples for the Determination of Chlorinated Biphenyl Congeners by
USEPA Method 1668A
S-MN-H-014
Preparation and Analysis of Samples for the
Determination of Polybrominated Diphenyl Ether Congeners
S-MN-H-016
RapidScreen Analysis of Samples for PCDDs and PCDFs S-MN-H-017
Determination of Anions by Ion Chromatography S-MN-I-301
Measurement of Solids in Water and Wastewater S-ALL-I-014
Measurement of pH in Water, Soil, and Waste S-ALL-I-015
TCLP/SPLP S-MN-I-312
Inductive) Coupled Plasma Atomic Emission Spectroscopy RCRA S-MN-I-313
Water Extraction of Soil S-MN-I-334
Hardness b Calculation S-MN-I-338
Biochemical Oxygen Demand (BOD) S-MN-I-348
COD-Titrimetric, Low Level S-MN-I-351
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SOP Title SOP Number
Phenols S-MN-1-354
Oil & Grease - 1664 S-MN-1-357
Hexavalent Chromiumin in Water, Wastewater, and Soil S-MN-1-358
Mercury im Liquid and Solid/Semis-Solid Waste S-MN-1-359
Alkalinity, Titrimetric S-MN-1-365
Total Cyanide in Water S-MN-1-366
Percent Solids Moisture S-MN-1-367
Digest Procedure for Aqueous Samples to be Analyzed b Induct Coupled Plasma SW-846 S-MN-1-458
Metals Preparation for Solid samples, Wipes and Filters S-MN-1-460
Fluoride in Water and Wastewater S-MN-1-470
Chemical Oxygen Demand COD in Water, Wastwaters and Industrial Wastes S-MN-1-472
Total Phosphorus in Water S-MN-1-473
Specific Conductivity S-MN-1-474
Total Cyanide in Soil S-MN-1-476
Ortho Phosphorus S-MN-1-477
Particulate Matter PM10 (Method 5 in the Atmosphere S-MN-1-484
Settleable Solids S-MN-1-486
Analysis of Air Samples b EPA Method 29 S-MN-1-487
Metals Analysis by ICP/MS - Method 6020 and 200.8 S-MN-1-492
Standard Test Method for Screening Apparent Specific Gravity and Bulk Density Waste S-MN-1-493
Determination of Total Recoverable Phenolics b Flow Injection Colorimet S-MN-1-494
Operation and Maintenance of the MDS-2100 Microwave S-MN-1-499
Turbidity in Water S-MN-1-501
Chlorine, Total Residual in Water S-MN-1-502
Use and Maintenance of the Konelab S-MN-1-507
Determination of Nitrate/Nitrite in surface and wastewaters by Flow Injection Analysis with the Konelab
(Low Flow Method)
S-MN-1-508
Determination of Chloride by Konelab S-MN-1-509
Determination of Sulfate b Konelab S-MN-1-510
Determination of Ammonia b Konelab Analysis, Colorimetr S-MN-1-511
Determination of Nitrite b Konelab S ectro photometric Method S-MN-1-514
Amenable Cyanide and Weak Dissociable Cyanide in Water S-MN-1-515
Paint Filter Liquids Test S-MN-1-516
Mercury in End Caps and Glass Samples S-MN-1-517
Gravimetric Determination of Oil and Grease b SPE S-MN-1-520
Determination of Perchlorate by IC S-MN-1-521
Cyanide Extraction Procedure for Solids and Oils S-MN-1-522
Preparation of Aqueous Samples for ICPMS Analysis by Method 3030C S-MN-1-523
System Security and Integrity S-ALL-IT-001
Back U Policy S-ALL-IT-002
Data Archiving S-MN-L-106
Reagent Water Quality S-MN-L-110
Generation of EDD S-MN-L-112
Handling and Analysis of North Carolina Samples S-IVIN-L-1 13
Preventative, routine, and non-routine maintenance S-MN-L-114
Common Laboratory Calculations and Statistical Evalation of Data S-MN-L-125
Data Reduction, Validation, and Reporting in the Env Lab S-MN-L-132
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SOP Title SOP Number
Out of Specification Investigation S-MN-L-133
Syringe Technique S-MN-L-139
Procedure for Handling Aqueous Organic Extractable Samples Containing Sediment S-MN-L-142
Total Coliform Bacteria S-MN-MB-001
Fecal Coliform by MF S-MN-MB-002
Heterotro hic Plate Count S-MN-MB-003
Total Coliform Bacteria b MF S-MN-MB-005
Sample Container Sterility Verification S-MN-MB-006
Method For Sonicator Tuning S-MN-0-414
Determination of Polynuclear Aromatic Hydrocarbons in Soil (8310) S-MN-0-419
The Determination of Specific Aromatic Compounds and Gasoline Range Organic in Water S-MN-0-427
Analysis of Polychlorinated Bi hen Is in Oil, Soil, Water, Wipe and Air Matrixes S-MN-0-432
Extractable Base/Neutral and Acid Organic Compounds in Liquid, Solid, and TCLP Matrices by Gas
Chromatography/Mass Spectrometry Capillary Column Technique
S-MN-0-436
Determination of Pol nuclear Aromatic Hydrocarbons in Water 8310 and EPA 610 S-MN-0-449
Cleaning Glassware in the Organic Laboratory S-MN-0-465
Determination of Diesel Range Organics in Water (Wisconsin modified DRO) S-MN-0-466
Determination of Diesel Range Organics in Soil (Wisconsin modified DRO) S-MN-0-467
Determination of Or ano hos horus Pesticides in Water and Soil MN.De t.of AG list 1 S-MN-0-471
The Determinaiton of Specific Aromatic Compounds and Gasoline Range Organics in Soil S-MN-0-487
Determination of Diesel Range Organics In Water & Soil SW8015 (Modified) S-MN-0-489
Determination of Acid Cleanup of PCB Extracts S-MN-0-494
Sonication Extraction Technique SW3550 for Base/Neutral and Acid Compounds S-MN-0-495
Continuous Liquid-Liquid Extraction SW3520 for Base/Neutral and Acid Compounds S-MN-0-496
Spike Verification in the Organic Prep Lab S-MN-0-497
Preparation of Anhydrous Sodium Sulfate for Extraction Purposes S-MN-0-500
Nitrogen Evaporation Technique S-MN-0-503
Sample Concentration Technique S-MN-0-504
Continuous Liquid-Liquid Extraction SW3520 for Pol aromatic Hydrocarbons b 8270-SIM S-MN-0-506
8270-L Extractable Base/Neutral and Acid Organic Compounds in Water and Liquid Matrices by GC/MS
Capillary Column Technique w/Selective Ion Monitoring
S-MN-0-507
Solvent Exchange into Hexane S-MN-0-509
Sample Conversion to Acetonitrile S-MN-O-510
Analysis of Volatile Organic Compounds by GC/MS Method 8260 S-MN-0-521
Purgeable Total Petroleum Hydrocarbons in Water (8015 Mod / CA LUFT/ NWTPH/OA-1) S-MN-0-525
Copper Cleanup Procedure for Pesticides and Polychlorinated Bi hen Is S-MN-0-527
Analysis of Volatile Organic Compounds b GC/MS Method 624 S-MN-0-529
Extractable Base/Neutral and Acid Organic Compounds in Liquid by EPA Method 625 S-MN-0-532
Analysis of Air samples by GC/MS - Method TO-13 S-MN-0-534
Continuous Liq/Liq extraction for Method 8270C (Dual pH) by SW 3520C S-MN-0-539
Soxhlet Extraction for PAH Analysis b GC/MS:SIM S-MN-0-540
Volatiles Sample Com ositin Procedure S-MN-0-541
Analysis of Volatile Organic Compounds in Water Method 524.2 S-MN-0-546
Extraction and Analysis of PCBs From Acid-Soluble Solids-Eastman Method S-MN-0-548
Extractable Base/Neutral and Acid Organic Compounds in Liquid b EPA Method 525 S-MN-0-549
Low Level Extractable Base/Neutral and Acid Organic Compounds by GC/MS Capillary Column
Technique
S-M N-O-552
Sample Management S-MN-C-001
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SOP Title SOP Number
Bottle Pre aratation S-MN-C-003
Internal Chain of Custody S-MN-C-005
Subcontracting Samples S-MN-C-004
Preparation of SOPs S-ALL-Q-001
Document Management S-ALL-Q-002
Document Numbering S-ALL-Q-003
Method and Instrument Detection Limit Studies S-ALL-Q-004
Purchasing of Laboratory Supplies S-AII-Q-005
Receipt and Storage of Laboratory Supplies S-ALL-Q-006
Laboratory Documentation S-ALL-Q-009
Performance Evaluation (PE)/Proficiency Testing PT Program S-ALL-Q-010
Audits and Inspection S-ALL-Q-011
Corrective Action/ Preventative Action Process S-ALL-Q-012
Support Equipment S-ALL-Q-013
Quality System Review S-ALL-Q-014
Manual Integrations S-ALL-Q-016
Subcontracting Samples S-ALL-Q-017
Monitoring Storage Units S-ALL-Q-018
Training Procedures S-ALL-Q-020
Sub-Sampling (Sample Homogenization) S-ALL-Q-021
3P Program: CIP S-ALL-Q-022
Standard and Reagent Pre artion and Traceability S-ALL-Q-025
Use and Operation of Lab Track System S-ALL-Q-028
Precision and Accuracy Measurement, Evaluation, and Trend Assessment S-MN-Q-205
Control of Hazardous Energy Program - Lockout/Ta out S-MN-Q-249
Method Validation and Modification Studies S-MN-Q-252
Procedure for Handling of USDA regulated soils S-MN-Q-253
Laboratory Spreadsheet Validation S-MN-Q-254
Estimation of Measurement Uncertainty S-MN-Q-255
Hazard Assessments S-ALL-S-001
Waste Handling S-ALL-S-002
aceAnalytical?
ATTACHMENT VI
PASI - MINNESOTA CERTIFICATION LIST
Quality Assurance Manual
Revision: 11.0
Page 67 of 73
State Agency Program Cert #
Alabama Dept of Environmental Dioxin-DW 40770
Mg mt
Alaska Dept. of Environmental Contaminated Sites UST-078
Conservation (6010B, 6020, 82608,
PCBs, PAHs)
Alaska Dept. of Environmental Dioxin-DW MN64-07
Conservation
Arizona Dept of Health Dioxin-DW, WW, HW AZ0014
Services
Arkansas Dept of Environmental Dioxins 88-0680
Quality
California Dept of Health Dioxin-DW, WW, HW 01155CA
Services Envir-DW, WW, HW
Colorado Dept. of Public Health Dioxin-DW Pace Analytical
& Environment
Connecticut Dept of Public Health Dioxins PH-0256
Delaware Health & Solical Dioxin-DW
Services
EPA Region 5 Water Division Dioxin-DW WD-15J
EPA Region 8 Water Division Dioxin-DW 8TMS-Q
Florida (NELAP) Dept of Health E87605
Services Diox-DW, WW, HW, Air
Envir-DW, WW, HW, Air
Georgia Environmental Dioxin-WW, HW via E87605
Protection Division NELAP
Georgia Dept of Natural Dioxin-DW 959
Resources
Guam Guam EPA Dioxin-DW Pace Analytical
Idaho Dept. of Health & Dioxin-DW Pace Analytical
Welfare
Hawaii Dept of Health Dioxin-DW SLD
ILLA ILLA ISO 17025 1706.01
Illinois Illinois EPA Dioxin-DW, HW, WW via 200011
NELAP
Indiana Dept of Health Dioxin-DW via EPA C-MN-01
Region 5
Iowa Dept.of Natural Envir.-DW, WW, UST 368
Resources
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Kansas Dept of Health and Dioxin-DW E-10167
Environment
Envir-DW, WW, HW
Kentucky Dept of Environmental Dioxin-DW 90062
Protection
Louisiana Department of Dioxin-WW, HW, Air 3086
Environmental Quality
Louisiana Department of Health Dioxin-DW LA050005
and Hospitals
Maine Dept of Human Dioxin-DW via EPA 2007029
Services Region 5
Maryland Dept. of Heath and Dioxin-DW 322
Mental Hygiene
Michigan Dept. of Public Health Dioxin-DW 9909
Minnesota Dept of Health Envir-DW, WW, HW 027-053-137
Dioxin-DW, WW, HW
Mississippi Dept. of Health and Dioxin-DW Pace
Environmental Control
Nebraska Dept. of Health & Dioxin-DW Pace
Human Services.
Nevada Health Division Dioxin-DW, WW MN_00064_2000_72
New Jersey Dept of Environmental Dioxin-DW, WW, HW MN002
Protection
Envir-WW, HW, Air
New Mexico NM Environment Dept. Dioxin-DW Pace
Drinking Water Bureau
New York Dept of Health Dioxin-DW, WW, Air 11647
Envir-Air
North Carolina Dept of Environment, Envir-WW, HW 530
Health and Natural
Resources
North Carolina State Public Health Dioxin-DW 27700
Laboratory
North Dakota Dept of Health and Envir-DW, WW, HW R-036
Consolidated Labs
Ohio Ohio EPA Dioxin-DW via EPA 4150
Region 5
Oklahoma Dept of Environmental Dioxin-DW D9921
Quality Envir-HW 9507
Oregon ELAP Dioxin-DW, WW, HW, Air MN200001
Enviro: Air
Pennsylvania Dept of Environmental Dioxin-DW, WW, HW 68-00563
Protection Envir: DW, WW, HW
aceAnalytical?
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Saipan (CNMI) Div. Of Environmental Dioxin-DW Pace Analytical
Quality
South Carolina Dept. of Health and Dioxin-DW, WW, HW 74003001
Environmental Control
Texas Department of Health Dioxin-DW, WW, HW T104704192-07-TX
Tennessee Dept of Health Dioxin-DW 2818
Envir-DW
Utah Department of Health Dioxin-DW, WW, HW ID# PAM
Account#
6126071700
Virginia Dept of General Dioxin-DW 251
Services
Washington Dept of Ecology Dioxin-DW, WW, HW C754
Envir-DW, WW, HW
Wisconsin Dept of Natural Dioxin-DW, WW, HW 999407970
Resources Envir-DW, WW, HW
West Virginia Dept of Health and Dioxin-DW 9952C
Human Resources
aceAnalytical?
ATTACHMENT VII
PASI - CHAIN OF CUSTODY
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Revision: 11.0
Page 70 of 73
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Quality Assurance Manual
;a',e I'lnalytical ` Revision: 11.0
Page 71 of 73
ATTACHMENT VIII
METHOD HOLD TIME, CONTAINER AND PRESERVATION GUIDE
PASI - MINNESOTA
Parameter Matrix Container Preservative Max Hold Time
2, 3, 7, 8-TCDD Soil 8 oz Glass Jar 90/40 Days
2, 3, 7, 8-TCDD Water 90/40 Days
Acidity Water 14 Days
Alkalinity Water 14 Days
Al ha Emitting Radium Isotopes Water HN03 180 days
Anions by IC, including Br, Cl, F, N02, N03,
S04
Water Br, Cl, F, S04 (28 Days)
N02, N03 48 Hours
Aromatic and Halogenated Volatiles Soil 5035 vial kit 14 days
Aromatic and Halogenated Volatiles Water HCl, Na2S203 14 Days
Bacteria, Total Plate Count Water Na2S203 24 Hours
Base/Neutrals and Acids Soil 8 oz Glass Jar 14/40 Days
Base/Neutrals and Acids Water HCl, Na2S203 7/40 Days
Base/Neutrals, Acids & Pesticides Water HCl, Na2S203 7/30 Days
BOD/cBOD Water 48 hours
BTEX/Total Hydrocarbons Air Summa Canister 14 Days
BTEX/Total Hydrocarbons Air Tedlar Bag 48 Hours
CARB 429 HRMS PAH Water 1 Liter 1 Yearto Extraction'
CARB 429 (HRMS PAH) Solid 4 or 8 oz. Jar 1 Year to Extraction'
CARB 429 HRMS PAH Tissue 4 or 8 oz. Jar 1 Year to Extraction'
Chloride Water 28 Days
Chlorinated Herbicides Soil 8 oz Glass Jar 14/40 Days
Chlorinated Herbicides Water HCl, Na2S203 14/28 Days
Chorine, Residual Water Analyze within 15 minutes
COD Water H2SO4 28 Days
Color Water 48 Hours
Condensable Particulate Emissions Air Solutions 6 Months
Cyanide, Reactive Water 28 Days

Cyanide, Total and Amenable
Water
NaOH 14 Days,
24 Hours if Sulfide resent
Diesel Range Organics Soil 8 oz Glass Jar 14/40 Days
Diesel Range Organics Water 7/40 Days
Dioxins & Furans Air PUF 30/45 Days
EDB & DBCP Water HCl, Na2S203 14 Days
Explosives Water 7/40 Days
Explosives Soil 8 oz Glass Jar 14/40 Days
Coliform, Fecal SM9221 D Water 100mL 10% sodium thiosulfate 6 hours
Coliform, Total SM9223B Water 100mL 10% sodium thiosulfate 24 hours
Ferrous Iron Water Immediate
Flashpoint/Ignitability Water 28 Days
Fluoride Water 28 Days
Gamma Emitting Radionuclides Water HN03 180 days
Gas Range Organics Water HCI 14 Days
Gasoline Range Organics Soil 5035 vial kit 14 days
Gross Alpha (NJ 48Hr Method) Water HN03 48 Hrs
Gross Alpha and Gross Beta Water HN03 180 days
Haloacetic Acids Water NH4CI 14/7 Days
Hardness, Total CaC03 Water HN03 6 Months
Hexavalent Chromium Water 24 Hours
Hydrogen Halide & Halogen Emissions Air Solutions 6 Months
Lead Emissions Air Filter/Solutions 6 Months
Low Level Mercury Water BrCI 90 days (if preserved and oxidized)
Mercury Soil 8 oz Glass Jar 28 days
Mercury Water HN03 28 Days
Metals Air Filters 6 Months
Metals Soil 8 oz Glass Jar 6 months
Metals (and other ICP elements) Water HN03 6 Months
Methane, Ethane, & Ethene Water HCI 14 Days
Methane, Ethane, Ethene Air Summa Canister 14 Days
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Parameter Matrix Container Preservative Max Hold Time
Methane, Ethane, Ethene Air Tedlar Bag 48 Hours
Method 23/TO9 Air Sampling Head 30 Days to Extraction'
Method 1631 E Water 500mL Glass Performed in the lab Oxidized in bottle within 28 days.
Nitrogen, Ammonia Water H2SO4 28 Days
Nitrogen, Kjeldahl Water H2SO4 28 Days
Nitrogen, Nitrate Water 48 Hours
Nitrogen, Nitrate & Nitrite Water H2SO4 28 Days
Nitrogen, Nitrite Water 48 Hours
Nitrogen, Organic Water H2SO4 28 Days
Non-Methane Organics Air Summa Canister 14 Days
Non-Methane Organics Air Tedlar Bag 48 Hours
Odor Water 24 Hours
Oil and Grease/HEM Water H2SO4 28 Days
Organchlorine Pesticides and PCB's Water HCI, Na2S2O3 7/40 Days
Organochlorine Pesticides & PCBs Air PUF 7/40 Days
Organochlorine Pesticides and PCB's Water HCI, Na2S2O3 7/40 Days
Organochlorine Pesticides and PCBs Soil 8 oz Glass Jar 14/40 Days
Or ano hos horous Pesticides Soil 8 oz Glass Jar 14/40 Days
Organo phosphorous Pesticides Water HCI, Na2S2O3 7/40 Days
Oxygen, Dissolved Probe Water Analyze within 15 minutes
Paint Filter Liquid Test Water N/A
Particulates Air Filters 6 Months
Permanent Gases Air Summa Canister 14 Days
Permanent Gases Air Tedlar Bag 48 Hours
H Water Analyze within 15 minutes
Phenol, Total Water H2SO4 28 Days

Phosphorus, Orthophosphate
Water Filter within 15 minutes,
Analyze within 48 Hours
Phosphorus, Total Water H2SO4 28 Days
Pol nuclearAromatic Hydrocarbons Air PUF 7/40 Days
Polynuclear Aromatic Hydrocarbons Soil 8 oz Glass Jar 14/40 Days
Polynuclear Aromatic Hydrocarbons Water HCI, Na2SZO3 7/40 Days
Radioactive Strontium Water HNO3 180 days
Radium-226 Radon Emanation Technique Water HNO3 180 days
Radium-228 Water HNO3 180 days
Silica, Dissolved Water 28 Days
Solids, Settleable Water 48 Hours
Solids, Total Water 7 Days
Solids, Total Dissolved Water 7 Days
Solids, Total Suspended Water 7 Days
Solids, Total Volatile Water 7 Days
Specific Conductance Water 28 Days
Stationary Source Dioxins & Furans Air XAD Trap 30/45 Days
Stationary Source Mercury Air Filters 6 Months, 28 Days for Hg
Stationary Source Metals Air Filters 6 Months, 28 Days for H
Stationary Source PM10 Air Filters 6 Months
Stationary Source Particulates Air Filter/Solutions 6 Months
Sulfate Water 28 Days
Sulfide, Reactive Water 28 Days
Sulfide, Total Water NaOH,ZnOAc 7 Days
Sulfite Water Analyze within 15 minutes
Surfactants Water 48 Hours
Total Organic Carbon (TOC) Water H2SO4 or HCI 28 Days
Total Organic Halogen (TOX) Water 14 Days
Tritium Water HNO3 180 days
Turbidity Water 48 Hours
Uranium Radiochemical Method Water HNO3 180 days
Volatiles Air Summa Canister 14 Days
Volatiles Air Tedlar Bag 48 Hours
Volatiles Air Summa Canister 14 Days
Volatiles Air Tedlar Bag 48 Hours
Volatiles Air Summa Canister 14 Days
Volatiles Soil 5035 vial kit 14 days
Volatiles Water HCI, Na2S2O3 14 Days
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Parameter Matrix Container Preservative Max Hold Time
Volatiles Water HCI, Na2S2O3 14 Days 7 un reserved
Volatiles Water HCI, Na2S2O3 14 Days
WIGRO Water 3 40 ml vials HCI 14 Days
WIGRO Solid 5035 vial kit See Note 14 Days
WIDRO Water 1 Liter HCI 7 Days to Extraction'
WIDRO Solid Tared 4 oz. Jar 14 Days to extraction'
1614 Water 1 Liter 1 Year to Extraction'
1614 Solid 4 or 8 oz. Jar 1 Year to Extraction'
1614 Tissue 4 or 8 oz. Jar 1 Year to Extraction'
1653 Water 2 L pH<2 H2SO4 30 Days to Extraction; 30 days to analysis
1668 Water 1 Liter 1 Year to Extraction'
1668 Solid 4 or 8 oz. Jar 1 Year to Extraction'
1668 Tissue 4 or 8 oz. Jar 1 Year to Extraction'
8015 McOH, Eoh Water 3 40 ml vials HCI 14 Days
8280 Water 1 Liter 30 Days to Extraction'
8280 Solid 4 or 8 oz. Jar 30 Days to Extraction'
8290 Solid 4 or 8 oz. Jar 30 Days to Extraction'
8290 Water 1 Liter 30 Days to Extraction'
8290 Waste 2 oz 30 Days to Extraction'
40 Days from Extraction to Analysis. (EPA 1613, W1 DRO)
45 Days from Extraction to Analysis (SW8290, 1668, 8280 and Method 231T09)
Note: 5035 kit contains 2 vials water, preserved by freezing or 2 vials aqueous NaHSO4 preserved at 4°C and 1 vial McOH
preserved at 4°C and 1 vial unpreserved at 4°C.
aceAnalytical "
www.pace/abs.com
Pace Analytical Services, Inc.
1700 Elm Street, Suite 200
Minneapolis, MN 55414
Phone: [phone]
Fax: [phone]
STANDARD OPERATING PROCEDURE
Preparation and Analysis of Samples for the
Determination of Chlorinated Biphenyl Congeners by
USEPA Method 1668A
SOP NUMBER:
EFFECTIVE DATE:
SUPERSEDES:
S-MN-1-1-014-Rev.08
Date of Final Signature
MN-1-1-014-rev.7
APPIV) AL
{
QuaJity Manager Tate
ANNUAL REVIEW
SIGNATURES BELOW INDICATE NO CHANGES HAVE BEEN MADE SINCE APPROVAL. SOP IS VALID FOR ONE YEAR FROM DATE OF LAST SIGNATURE.
Signature
Signature
Title
Title
Date
Date
©2002- 2007, Pace Analytical Services, Inc. This Standard Operating Procedure may not be reproduced, in part or in full,
without written consent of Pace Analytical Services, Inc. Whether distributed internally or as a "courtesy copy" to clients or
regulatory agencies, this document is considered confidential and proprietary information.
Any printed documents in use within a Pace Analytical Services, Inc. laboratory have been reviewed and approved by the persons
listed on the cover page. They can only be deemed official if proper signatures are present.
This is COPY# 7 distributed on 16NOV2007 by __AO and is CONTROLLED or X UNCONTROLLED.
S-MN-H-014-Rev.08
Table of Contents
1. PURPOSE ...............................................................................................................................1
2. SCOPE AND APPLICATION .............................................................................................1
3. SUMMARY OF METHOD ..................................................................................................1
4. INTERFERENCES ................................................................................................................1
5. SAFETY ..................................................................................................................................2
6. DEFINITIONS .......................................................................................................................3
7. RESPONSIBILITIES AND DISTRIBUTION ....................................................................3
8. SAMPLE COLLECTION, PRESERVATION AND HANDLING ..................................3
9. EQUIPMENT AND SUPPLIES ...........................................................................................4
10. REAGENTS AND STANDARDS ........................................................................................6
11. CALIBRATION .....................................................................................................................9
12. PROCEDURE ......................................................................................................................11
13. QUALITY CONTROL ........................................................................................................29
14. METHOD PERFORMANCE .............................................................................................32
15. POLLUTION PREVENTION AND WASTE MANAGEMENT ....................................32
16. REFERENCES .....................................................................................................................33
17. TABLES, DIAGRAMS, FLOWCHARTS, APPENDICES, ADDENDA ....................... 33
18. REVISIONS ..........................................................................................................................33
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 1 of 63
1. PURPOSE
To describe the standard operating procedure for the preparation, analysis, processing and reporting of
samples for the determination of chlorinated biphenyls using USEPA Method 1668A.
2. SCOPE AND APPLICATION
Method 1668, Revision A (1668A) is for determination of chlorinated biphenyl (CB) congeners in water, soil,
sediment, biosolids, tissues, and other sample matrices by high resolution gas chromatography/high resolution
mass spectrometry (HRGC/HRMS). The CB congeners that can be determined by this method are the 12
PCBs that have been designated as toxic plus the remaining 197 CBs, approximately 125 of which are
sufficiently resolved by this method to be reported as individual congeners. Approximately 70 congeners are
reported as mixtures of co-eluting isomers. PCB toxicity equivalents can also be determined and the total
amount of each homologue by level of chlorination can be estimated. See Attachment 3 for the full list of
congeners.
3. SUMMARY OF METHOD
Stable isotopically labeled analogues of 27 of the PCBs are added to each sample. Samples containing course
solids are prepared for extraction by grinding or homogenization. Water samples are extracted in separatory
funnels. Soils and other finely divided solids are extracted using Soxhlet extraction apparatus. Tissue samples
are mixed with anhydrous sodium sulfate, and extracted in a Soxhlet extractor.
After extraction, a labeled cleanup standard is spiked into the extract prior to cleanup steps. Sample cleanup
steps may include back extraction with acid and/or base, as well as silica gel, florisil, gel permeation and
activated carbon chromatography. After cleanup, extracts are spiked with isotopically labeled recovery
standards that are used to measure the portion of labeled analogues that survived the extraction and cleanup
processes. The extracts are the analyzed by HRGC/HRMS to determine the concentrations of PCBs.
4. INTERFERENCES
4.1 Most samples analyzed for PCB content contain other organic compounds that will interfere with or
contaminate the mass spectrometric instrumental system. Therefore, after initial extraction, extracts are
taken through the enrichment steps outlined in the "Extract Enrichment" section of this procedure.
Performance of the optional enrichment steps is determined based on the extract appearance or the initial
analytical results.
4.2 Matrix interferences may be caused by contaminants co-extracted from the sample and will vary
considerably from source to source.
4.3 Some samples may contain levels of interfering compounds which overload the analyte enrichment
columns. Consult senior analytical personnel for alternate procedures should this occur.
4.4 Rigorous glassware cleaning techniques must be used and method blank data must be monitored to
evaluate the effectiveness of the glassware cleaning techniques.
4.5 HPLC grade solvents should be used for extractions. Solvents having new lot numbers should be
screened for contamination prior to use by analyzing a solvent blank by the applicable analytical methods.
4.6 Raw data from all blanks, samples, and spikes are evaluated for interferences. Determine if the source of
interferences is in the preparation and/or cleanup of the samples and take corrective action to eliminate
the problem.
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4.7 If chromatographic interferences are present, the height from the smaller signal of the pair is used along
with the theoretical ratio to determine the height of the second ion. These values are then used to
calculate the estimated maximum possible concentration.
4.8 Some interference may be reduced by analysis of a dilution of the extract.
4.9 Clean up of tissue samples - The natural lipid content of tissue can interfere in the analysis of tissue
samples for chlorinated biphenyls by overwhelming the capacity of the chromatographic columns used
for cleanup of the sample extracts. Lipids must be removed by acid washes or by the anthropogenic
isolation column procedure followed by gel permeation chromatography.
5. SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has not been fully established. Each
chemical should be regarded as a potential health hazard and exposure should be as low as reasonably
achievable. Cautions are included for known extremely hazardous materials
5.2 Each laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference file of Material Safety Data Sheets
(MSDS) should be made available to all personnel involved in the chemical analysis. The preparation of
a formal safety plan is also advised.
5.3 MSDS sheets are located at the front desk and should be consulted prior to handling samples and
standards.
5.4 Only highly trained personnel thoroughly familiar with handling and cautionary procedures and who
understand the risks associated with this procedure will handle all PCB standards.
5.5 Neat PCBs require the use of respirators and are not to be handled in the laboratory.
5.6 Protective equipment must be worn when working with standards or samples under this procedure. This
includes safety glasses, laboratory coat, and throwaway plastic gloves. Plastic sleeves, aprons and other
protective equipment are also readily available if needed. All steps of this procedure must be performed
in a properly operating fume hood except those noted.
5.7 All personnel performing any part of this procedure must be properly trained in removing contaminated
materials and properly disposing of them. This includes an awareness of personal hygiene as it pertains to
the laboratory, personal actions as they affect coworkers, etc.
5.8 All samples analyzed at the Minneapolis chemistry facility are held until analytical results have been
reported. Samples containing PCBs above the allowable levels are labeled, segregated, and disposed of
by personnel trained in handling toxic waste. Similarly grossly contaminated waste items including
pipette tips and other laboratory equipment are segregated, collected in lined waste containers, properly
labeled, and disposed of in accordance with hazardous waste regulations.
5.9 Laboratory staff will wipe down a representative area of specified fume hoods at least annually using pre-
sterilized gauze and hexane. These wipes will be analyzed according to this method to ensure that good
laboratory practices are observed at all times. The results of the wipes will be archived for reference.
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6. DEFINITIONS
6.1 Definitions are located in the Glossary section of the PASI Quality Manual.
7. RESPONSIBILITIES AND DISTRIBUTION
7.1 Personnel
7.1.1 All personnel involved with sample preparation and analysis are responsible for adherence to this
SOP. A controlled copy will be available for review and consultation within the area methods
manual.
7.1.2 Personnel are responsible for ensuring that any deviations to this SOP are reported to the
laboratory manager.
7.2 Laboratory Manager
7.2.1 The laboratory manager is responsible for ensuring adherence to this SOP and will receive a
controlled copy of this SOP.
7.2.2 The laboratory manager is responsible for performing a biennial review of the SOP and reporting
any required revisions to the Quality Assurance Office.
7.3 Quality Assurance Office
7.3.1 The QA Office is responsible for conducting laboratory audits to monitor adherence to this and
other SOPS. Results of the audit will be reported to Management.
7.3.2 The QA Office is responsible for ensuring that all revisions to the SOP are implemented.
7.3.3 The QA Office is responsible for maintaining the original and complete distribution records.
7.4 Revisions
7.4.1 This SOP will be reviewed on an annual basis at a minimum, and any required revisions will be
incorporated.
8. SAMPLE COLLECTION, PRESERVATION AND HANDLING
8.1 SAMPLE COLLECTION
8.1.1 Sample size - One liter of water samples containing less than or equal to 1% solids should be
extracted in separatory funnels. Aqueous or solid samples containing greater than 1% solids
should be considered as solids and sufficient volume extracted to provide a dry weight of 10
grams (except for tissue samples and other samples noted to be reported on an as received basis).
One-gram aliquots are typically extracted for waste samples and samples suspected to contain
high analyte levels. One hundred milligram aliquots are typically used for oil-based samples, and
100 mL for milk samples.
8.2 SAMPLE PRESERVATION AND HANDLING
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8.2.1 Collect samples in glass containers following conventional sampling practices.
8.2.2 Maintain aqueous samples at 4°C ± 2°C under darkness from the time of collection until
extraction. If residual chlorine is present in aqueous samples (from chlorinated sources), add 80
mg sodium thiosulfate per one liter of water.
8.2.3 Preserve aqueous samples to pH 2-3 with sulfuric acid.
8.2.4 Tissue and other solid samples are stored frozen at <-10°C under darkness.
8.2.5 All sample extracts are stored at <-10°C until analysis.
8.3 HOLDING TIMES
8.3.1 There are no demonstrated maximum holding times associated with the CBs in aqueous, solid,
semi-solid, tissue or other sample matrices. If stored in the dark at 0-4 C and preserved as given
above (if required), aqueous samples may be stored for up to one year. Similarly, if stored in the
dark at <-10°C, solid, semi-solid, multi-phase, and tissue samples may be stored for up to one
year. Sample extracts may also be stored for up to one year in the dark at <-10°C.
8.4 CRITERIA FOR ACCEPTANCE/REJECTION OF SAMPLES
8.4.1 Samples are to be rejected if information allowing determination of the applicable test and client
information cannot be obtained.
8.4.2 If sample integrity has been compromised, the client must be contacted for instructions and
permission to proceed with analysis. The client's comments and instructions are documented as
part of routine laboratory policy.
9. EQUIPMENT AND SUPPLIES
9.1 Sample bottles - 1 Liter glass amber bottles for liquids, which contain less than 1% solids; 500 mL wide
mouth (or smaller) glass amber bottles for solid and sludge. All bottles are purchased pre-cleaned from
the vendor. If glass amber bottles are not available, samples shall be protected from the light. All bottles
should have Teflon lined caps. Laboratory cleaned bottles may be substituted for pre-cleaned bottles.
Bottles should be detergent washed, then solvent rinsed and baked at 450°C for a minimum of one hour.
9.2 10 mL open top glass vials
9.3 2 dram vials with Teflon-lined screw caps
9.4 Reacti vial - 2 mL borosilicate glass
9.5 1 Liter graduated cylinder
9.6 Balances - 0.01g and 0.0001g
9.7 Drying oven
9.8 Soxhlet extraction apparatus
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9.9 Thimble, 33 x 90 mm to fit Soxhlet
9.10 Heating mantle
9.11 Beakers, 50, 250, 500, 2000 Ml
9.12 Stainless steel spatulas
9.13 Assorted syringes and/or Eppendorf digital pipettes
9.14 Filtration apparatus
9.15 Glass chromatographic column - 5 3/4" disposable Pasteur pipets
9.16 40 mL vial with caps
9.17 60 mL vial with caps with septa
9.18 Glass funnel, 125-250 mL
9.19 Glass fiber filter paper (Whatman GF/D or equivalent)
9.20 Centrifuge apparatus - capable of rotating 500 mL centrifuge bottles or 15 mL tubes at 5000 rpm
minimum
9.21 Disposable Pasteur pipettes
9.22 Disposable serological 10 mL pipettes
9.23 500 mL Kuderna Danish (KD) concentrator apparatus
9.24 Teflon boiling chips - pre-rinsed with methylene chloride
9.25 Water bath, ultrasonic
9.26 Desiccator
9.27 Nitrogen evaporation system with variable flow rate
9.28 Volumetric flasks - 5 mL, 10 mL, 15 mL, 20 mL, 25 mL and 100 mL
9.29 Teflon tape
9.30 Low volume autosampler vial with crimp caps
9.31 Sodium hydroxide - reagent grade. Dissolve 40 g NaOH in 1L reagent water.
9.32 Potassium Phosphate - reagent grade - Dissolve 68.05 g KHZPO4 in 1 L reagent H2O
9.33 Sulfuric acid - reagent grade (sp gravity 1.84)
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9.34 Silica gel -chromatographic grade, 60-100 mesh
9.35 Celite - reagent grade
9.36 Anhydrous sodium sulfate - Rinse with methylene chloride (20 mL/g) and bake at 130°C for 1 hour
minimum. Store baked anhydrous sodium sulfate in oven until use. Cool prior to use.
9.37 Carbon (AX-21 or equivalent)
9.38 Solvents - Acetone, toluene, hexane, cyclohexane, nonane, methanol and methylene chloride. All
solvents must be distilled in glass and pesticide grade.
9.39 Alumina - activity grade
9.40 White quartz sand 60/70 mesh
9.41 Diatomaceous earth
9.42 Reference matrices
9.42.1 Reagent water
9.42.2 Playground sand or similar material which is free of target compounds; may be prepared by
extraction with methylene chloride and/or baking at 450°C for 4 hours.
9.42.3 Corn oil, tested to be analyte free
9.42.4 Filter paper - Gelman type A or equivalent
9.42.5 Mineral Oil
9.42.6 Milk, whole
9.43 Individual standards prepared as described in the "Procedure" section of this SOP.
9.44 Micromass Ultima Autospec Double Focusing High Resolution GC/MS
10. REAGENTS AND STANDARDS
10.1 Standards and working solutions are prepared from or compared to certified standards or purchased as
certified premixed standards. All standards are valid for 1 year from date opened (or prepared). All
standards are stored in glass bottles and stored at <-IOoC. Standards may be re-verified by comparison to
a valid native analyte solution. The final concentrations determined for any solution being re-verified
must meet the continuing calibration limits for the analytes in that solution and are valid for 1 year from
the date of verification.
10.2 The preparation of standards and working solutions is thoroughly documented in the appropri ate
standards notebook. Such documentation allows the traceability of each solution to a certified, purchased
solution.
10.3 Preparation of native (unlabeled) stock solutions
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10.3.1 Native Toxics/LOC stock solution -Prepare to contain the native Toxics and LOC CBs at the
concentrations shown in Table 3, or purchase Accu-Standard M1668A-C-NT-LOC-WD-GCPC or
equivalent. If additional CBs are to be determined by isotope dilution (e.g. 170 and 180), include
the additional native compounds in this solution.
10.3.2 Native 209 CB congener stock solutions (These five solutions contain the CB isomers necessary
to calibrate the SPB-octyl column. If a column other than SPB-octyl is used, mixtures must be
prepared that will allow separation of all 209 congeners on that column). For the SPB-octyl
column, prepare the five solutions with the congeners listed in Table 4 at the concentrations
shown in Table 3 or purchase Accu-Standard M-1668A-1, M- 1668A-2, M-1668A-3, M-1668A-4,
M-1668A-5, or equivalent.
10.3.3 Combined 209-congener stock solution -Combine equal volumes of the five standards in the
above section (2) to form a stock solution containing all 209 CB isomers at 0.5-1.5 µg/mt.
10.3.4 Sonicate solutions for five minutes and transfer into clean, labeled vials. Identification should
include: ID#, log #, vial numbers, preparation date and preparer's initials.
10.3.5 Seal with Teflon tape, mark the meniscus (now and after each use) and store in the standards
freezer.
10.3.6 Record all standard preparation information in Dioxin Standard Notebook.
10.4 Preparation of Labeled Compound Stock Solutions
10.4.1 Labeled Toxics/LOC/Window-defining stock solution - Prepare in nonane at the concentrations
shown in Table 3 or purchase Cambridge Isotope Laboratories (CIL) EC-4977 or equivalent. If
additional CBs are to be determined by isotope dilution (e.g. 170 and 180), include the additional
labeled compounds in this solution.
10.4.2 Labeled cleanup standard stock solution - Prepare labeled CBs 28, 111, and 178 in nonane at the
concentrations shown in Table 3 or purchase CIL EC-4978 or equivalent.
10.4.3 Labeled injection internal standard stock solution - Prepare labeled CBs 9, 52, 101, 138, and 194
in nonane at the concentrations shown in Table 3 or purchase CIL EC-4979 or equivalent.
10.4.4 Sonicate each solution for five minutes and transfer into clean labeled vials. Identification should
include: ID#, log #, vial numbers, preparation date and preparer's initials.
10.4.5 Seal with Teflon tape, mark the meniscus (now and after each use) and store in the standards
freezer.
10.4.6 Record all standard preparation information in Dioxin Standard Notebook.
10.5 Preparation of calibration standards
10.5.1 Standards for initial calibration (ICAL solutions CS-1 through CS-5) - The compounds
contained in these solutions are shown in Table 5. These solutions should be purchased as CIL
EC-4976 or equivalent. Alternatively, the solutions of native and labeled congeners from
sections C and D can be combined and diluted to produce the calibration solutions shown in
Table 5. The CS-3 solution (CIL EC-4976-3) is used for calibration verification.
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10.5.2 Diluted individual congener solutions - The five solutions from section C-2 are diluted mixed
with labeled standards and then analyzed individually. They allow the establishment of retention
time and other data for each of the 209 congeners on the SPB-octyl column. The elution order of
the congeners present in each solution is given in Table 4. The five solutions of diluted
standards are made by combining an aliquot of one of the native stock solutions (from C-2) with
the labeled Toxics/LOC /window defining stock solution (D-1), the Labeled cleanup standard
stock solution (D-2) and the Labeled injection internal standard stock solution (D-3), to produce
concentrations of 100ng/ml for the labeled compounds and 25, 50, and 75 ng/ml for the MoCB-
TrCB, TeCB-HpCB, and OcCB-DeCB congeners respectively as shown in Table 3.
10.5.3 Diluted combined 209 congener solution - (combines all 209 congeners with the labeled
standards to allow single point calibration of the congeners which are not included in the 5-point
calibration, and also establishes average response factors for co-eluting isomers) - Mix an aliquot
of the combined 209 congener solution (C-3) with aliquots of the Labeled Toxics/LOC/window
defining stock solution (D-1), the Labeled cleanup standard stock solution (D-2) and the Labeled
injection internal standard stock solution (D-3) to produce the same concentrations as in the
individual mix solutions in E-2 above.
10.5.4 Sonicate for five minutes and transfer each solution into pre-rinsed vials labeled with ID#, log #,
preparation date, and preparer's initials.
10.5.5 Seal with Teflon tape, mark the meniscus (now and after each use) and store in the standards
freezer.
10. 5.6 Record all standard preparation information in Dioxin Standard Notebook.
10.6 Preparation of spiking solutions
10.6.1 Native Toxics/LOC standard spiking solution (used for determining initial and ongoing precision
and recovery). Dilute the Native Toxics/LOC stock solution (C-1) with acetone to produce a
concentration of the Toxics at 1 ng/ml as shown in Table 3. When 1 ml of this solution is spiked
into the IPR or OPR and concentrated to a final volume of 20 uL, the concentration in the final
volume will be 50 ng/ml. Prepare only the amount necessary for each sample batch.
10.6.2 Labeled Toxics/LOC/window defining standard spiking solution (spiked into each sample as well
as blanks and spikes to measure recovery). Dilute the Labeled Toxics/LOC/window defining
stock solution (D-1) with acetone to produce a concentration of the labeled compounds at 2
ng/ml, as shown in Table 3. When 1 ml of this solution is spiked into an IPR, OPR, blank or
sample and concentrated to a final extract volume of 20 ul, the concentration in the final extract
will be 100 ng/ml. Prepare only the amount necessary for each sample batch.
10.6.3 Labeled cleanup standard spiking solution (spiked into each extract prior to cleanup to measure
the efficiency of the cleanup process). Dilute the Labeled cleanup standard stock solution (D-2)
in methylene chloride to produce a concentration of the cleanup standards at 2 ng/ml, as shown in
Table 3. When 1 ml of this solution is spiked into a sample extract and concentrated to a final
volume of 20 µl, the concentration in the final extract will be 100 ng/ml. Prepare only the
amount necessary for each sample batch.
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10.6.4 Labeled injection internal standard spiking solution (added to each concentrated extract prior to
analysis). Dilute (1:25) the Labeled injection internal standard stock solution (D-3) in nonane to
produce a concentration of the injection internal standards at 200 ng/ml (a 1:5 dilution of the level
shown in Table 3). When 10 µl of this solution is spiked into a 20-µ1 extract, the concentration of
each injection internal standard will be nominally 100 ng/ml.
10.7 Accuracy and stability of the standard solutions
10.7.1 A QC check sample should be obtained from a source independent of the calibration standards to
verify the accuracy of the determination. Alternately, the spiking solutions should be compared
to standards from a different source to verify their continuing accuracy.
II. CALIBRATION
11.1 Establish the operating conditions necessary to meet the retention time (RT) and relative retention time
(RRT) requirements for the CBs listed in Table 2.
11. Suggested GC operating conditions:
Injector temperature
Interface temperature
Initial temperature
Initial time
Temperature program
Final time
270°C
280°C
140°C
2 minutes
150°C @ 15°C/min, hold 6 min, then 280°C @ 2.5°C/min
6 minutes
The GC conditions may be optimized for compound separation and sensitivity. Once optimized,
the same GC conditions must be used for analysis of all standards, blanks, IPR and OPR
standards, and samples.
11. 1.2 Retention time calibration for the CB congeners
11.1.2.1 Separately inject each of the diluted individual congener solutions (E-2). Establish the
beginning and ending retention times for the scan descriptors in Table 7. Scan descriptors
other than those listed in Table 7 may be used provided the MLs in Table 2 are met.
11.1.2.2 The absolute retention time of CB 209 should exceed 55 minutes on the SPB-octyl column;
otherwise, the GC temperature program must be adjusted and this test repeated until the
minimum retention time criterion is met. If a GC column other than the SPB-octyl column
is used, a similar minimum retention time specification must be established for that column
so that interferences that may be encountered in environmental samples will be resolved
from the analytes of interest. This specification is considered to be met if the retention time
of CB 209 is greater than 55 minutes on the alternate column. It is anticipated that the
minimum retention time for CB 209 will be reduced to 45 minutes in the next method
revision. It is acceptable to adopt the revised time immediately upon promulgation.
11.1.2.3 Inject the diluted combined 209-congener solution (E-3). Adjust the chromatographic
conditions and scan descriptors until the congeners elute within the acquisition windows,
and the following column performance specifications are met if an SPB octyl column is
used:
GC resolution of all Toxic congeners except 156 and 157
GC resolution of 156/157 from all other congeners
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GC resolution of congeners 34 and 23
GC resolution of congeners 187 and 182
Congeners 156 and 157 elute within 2 seconds
11.1.2.4 Confirm that the group switch times occur when no congeners are eluting
11.1.3 Mass spectrometer resolution
11.1.3.1 Using PFK, tune the mass spectrometer to approximately 10000 resolving power (10%
valley) at any significant PFK fragment in the range of 300-350. The amount of PFK
should be adjusted so that the amplitudes of all lock masses monitored are less than 10% of
full-scale deflection of the instrument.
11.1.3.2 Obtain a selected ion current profile (SICP) at the two exact masses specified in Table 7 for
each native congener and labeled standard. Because of the extensive mass range covered in
each function, it may not be possible to maintain 10000 resolution across the entire range.
Therefore, resolution must be at least 8000 throughout the mass range and must be 10000
resolution in the center of the mass range for each function.
11.2 Calibration Standards Acceptance Criteria
11.2.1 Standards must meet the following requirements before analyzing samples.
11.2.1.1 Ratios for the calibration standards should be within 15% of theoretical values (Table 8).
Values outside of the 15% limit may be accepted. However, the potential impact of the
variation shall be discussed in the narrative of the report. Any outliners are also flagged in
AutoPro.
11.2.1.2 Initial calibration relative standard deviations must be less than 20% for the native isomers
with a corresponding internal standard. The remaining native isomers and the labeled
isomers do not have a required range. However, relative standard deviations of less than
30% should be targeted for these compounds. The diluted combined 209-congener solution
is also analyzed at the time of initial calibration and each analysis shift to generate response
factors and retention time ranges for the remaining native isomers.
11.2.1.3 A continuing calibration standard (VER) is analyzed at the beginning of each day and must
yield response factors within 30% (native isomers), 50% (internal standards) and -40% to
+30% (cleanup standards) of the initial calibration.
11.2.1.4 Each compound in the VER must be present with a signal to noise ratio of at least 10.
11.2.1.5 All peaks for a given PCB level of chlorination must elute within the window(s) set up for
that particular class (determined from the window defining mix, which contains first and
last eluting isomers).
11.2.1.6 Native compounds must elute within the expected elution time relative to the elution times
of the corresponding internal standards.
11.2.1.7 Column performance specifications must be met. For the SPB Octyl column they are:
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11.2.1.7.1 Retention time for PCB 209 > 55 minutes (maybe revised down to 45 minutes upon
next method revision).
11.2.1.7.2 PCB isomers 34 and 23 must be resolved, isomers 187 and 182 must be resolved,
isomers 156 and 157 must co-elute. These criteria apply to the analysis of the 209
PCB solution.
12. PROCEDURE
12.1 PREPARATION PRIOR TO SAMPLE EXTRACTION
12. 1.1 Aqueous samples containing one percent solids (or less) are extracted in separatory funnels.
12.1.2 In samples expected or known to contain high levels of the PCBs, the smallest sample size
representative of the entire sample should be used, and the extract should be diluted, if necessary.
12.1.3 Determination of Percent Solids
12.1.3.1 Weigh 5-10 g of sample to three significant figures into a tarred weighing vessel.
12.1.3.2 Dry overnight (minimum of 12 hours) at 110 ± 5°C and cool in a desiccator. Reweigh.
12.1.3.3 % Solids = Wt dried sample (g) x 10 - Wt wet sample (g)
12.1.3.4 Data are recorded electronically and printed out as needed.
12.1.4 Soxhlet/Dean Stark Glassware Pre-extraction
12.1.4.1 Place 30-40 mL of toluene in the extractor and 200-250 mL in the flask along with
approximately 5-8 Teflon boiling chips.
12.1.4.2 Pre-extract the glassware by heating the flask until the toluene is boiling. When properly
adjusted, 1-2 drops of toluene per second will fall from the condenser tip into the receiver.
Extract the apparatus for 3 hours minimum (typically overnight).
12.1.4.3 After pre-extraction, disassemble the apparatus. Refill with 200-250 mL fresh extraction
solvent.
12.1.4.4 Extraction Vessel Pre-extraction (MAE)
12.1.4.4.1 Place 50 mL of toluene in the clean MAE cell with wellon tube.
12.1.4.4.2 Pre-extract the apparatus using the following program:
10 min ramp time, 115° C, 1000W
45 min extraction time, 115° C, 1000W
5 min cool time, 0° C, OW
10 min vent
Note: These conditions can be further optimized through method development testing
12.1.5 Aqueous Sample Preparation (<1% Solids)
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12.1.5.1 Mark the original level of the sample on the sample bottle for later determination of sample
volume. Weigh the sample in the bottle to ± 1 g on a top loading balance. Record this
weight.
12.1.5.2 Spike 1 mL of the Labeled Toxics/LOC/window defining standard spiking solution into the
bottle. Cap the bottle and mix by carefully shaking for 2 minutes. Allow to equilibrate for
1-2 hours with occasional shaking.
12.1.5.3 For each sample or sample set (up to 20) to be extracted during the same twelve-hour shift,
place two 1.0 L aliquots of reagent water in clean 1 L Erlenmeyer flasks. One additional
aliquot of reagent water may be used if a duplicate OPR sample is requested.
12.1.5.4 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). If they are requested, place the two 1.0 L aliquots of client-supplied
duplicate water samples in clean 1 L Erlenmeyer flasks.
12.1.5.5 Spike 1 mL of the Labeled Toxics/LOC/window defining standard spiking solution into
one reagent water sample. This aliquot will serve as the blank.
12.1.5.6 Spike 1 mL of Labeled Toxics/LOC/window defining standard spiking solution and 1 mL
of the Native Toxics/LOC standard spiking solution into the remaining reagent water
aliquot(s). This (they) will serve as the ongoing precision and recovery spike(s) or OPR(s).
Spike 1 mL of Labeled Toxics/LOC/window defining standard spiking solution and 1 mL
of the Native Toxics/LOC standard spiking solution into the client-supplied duplicate water
samples (if supplied and requested). These samples will serve as the matrix spike/spike
duplicate samples.
12.1.5.7 Assemble a Buchner funnel and a vacuum adapter on top of a clean 1 L Erlenmeyer flask.
Apply a vacuum to the flask and pour the entire contents of the sample bottle through a
glass fiber filter in the Buchner funnel, swirling the sample remaining in the bottle to
suspend any particulate. Rinse the bottles with three 60 mL portions of methylene chloride,
pouring each portion through the filter. Samples containing no particulate need not be
filtered; instead, quantitatively transfer the samples to separatory funnels. Treat the QC
samples in the same manner as the field samples.
12.1.5.8 If filtered, rinse any particulate off the sides of the Buchner funnel with small quantities of
methylene chloride.
12.1.5.9 Weigh the empty sample bottle on a top loading balance to ± 1 g. Determine the weight of
the sample by difference and note the weight on the extraction preparation sheet.
12.1.5.10 Save and extract the filter, particulate and filtrates as described below.
12.1.5.11 Preparation of Aqueous Samples containing >1% solids
12.1.5.12 Weigh a well-mixed aliquot of each sample sufficient to provide 10 g of dry solids (based
on the solids determination described above) into a clean beaker, pre-extracted thimble or
glass jar. In certain cases, i.e., sludge or waste matrices, this amount maybe modified to a
smaller aliquot to provide more workable extracts.
12.1.5.13 Spike each sample with 1 mL of the Labeled Toxics/LOC/window defining standard
spiking solution.
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12.1.5.14 For each sample or sample set (up to 20) to be extracted in the same twelve hour shift,
weigh two 10 g aliquots of clean sand and place each aliquot into a Soxhlet thimble. If an
additional OPR is requested, include an additional aliquot of reference matrix material.
(Sand is pre-extracted prior to use.)
12.1.5.15 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). Place the appropriate weight of client-supplied duplicate samples into clean
beakers or glass jars.
12.1.5.16 Spike one reference sample with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution. This aliquot will serve as the method blank.
12.1.5.17 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining standard
spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution. This (they)
will serve as the OPR(s).
12.1.5.18 Spike the client-supplied duplicate samples with 1 mL of the Labeled Toxics/LOC/window
defining standard spiking solution and 1 mL of the Native Toxics/LOC standard spiking
solution. These samples will serve as the matrix spike/matrix spike duplicate set (if
required).
12.1.5.19 If sample flows easily, assemble a Buchner funnel and a vacuum adapter on top of a clean
1 L Erlemneyer flask. Apply a vacuum to the flask and pour the aliquot through a glass
fiber filter in the Buchner funnel, swirling the sample remaining in the bottle to suspend
any particulate. Rinse the bottle 3 times with 60 mL of reagent water pouring each
aliquot through the filter.
12.1.5.20 The sample may otherwise be separated using a centrifuge, and the liquid fraction decanted.
With this procedure, the correct sample amount is first transferred into a different container
for centrifuging. After centrifuging, the entire solid portion is mixed with sodium sulfate
and transferred to a Soxhlet extraction thimble, as described for solid sample preparation.
12.1.5.21If filtered or centrifuged, rinse any particulate off the sides of the Buchner funnel or sample
container with small quantities of methylene chloride.
12.1.5.22 Save and extract the filtrates as described below. (If greater than 100 mL of water is
present, extract it in a separatory funnel and combine with the solid extract, otherwise
discard aqueous phase.)
12.1.6 Preparation of Multiphase Samples
12.1.6.1 Spike an appropriately sized aliquot of the sample with 1 mL of the Labeled
Toxics/LOC/window defining standard spiking solution.
12.1.6.2 For each sample or sample set (up to 20) to be extracted in the same eight hour shift, weigh
two 10 g aliquots of clean sand and place each aliquot into a Soxhlet thimble. If an
additional OPR is requested, include an additional aliquot of reference matrix material.
(Sand is pre-extracted prior to use.)
12.1.6.3 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). Place the appropriate weight of client-supplied duplicate samples into
clean beakers or glass jars.
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12.1.6.4 Spike one reference sample with 1 mL of Labeled Toxics/LOC/window defining standard
spiking solution. This aliquot will serve as the method blank.
12.1.6.5 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining standard
spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution. This (they)
will serve as the OPR spike(s).
12.1.6.6 Spike the client-supplied duplicate samples with 1 mL of the Labeled Toxics/LOC/window
defining standard spiking solution and 1 mL of the Native Toxics/LOC standard spiking
solution. These samples will serve as the matrix spike/matrix spike duplicate set (if
required).
12.1.6.7 Pressure filter the sample, blank and OPR spike aliquots through Whatman GF/D glass
fiber filter paper. If necessary, centrifuge these aliquots for 30 minutes at greater than
5000 rpm prior to filtration.
12.1.6.8 Discard aqueous phase. (If aqueous phase is 50 mL or greater, a separatory funnel
extraction is performed and the extract is combined with the extract form the solid
portion.) Remove any non-aqueous liquid (if present) and reserve for recombination with
the extract of the solid phase. Prepare the filter papers of the sample and QC aliquots for
particle size reduction and blending.
12.1.6.9 Prior to spiking, samples with particle size greater than 1 mm are subjected to grinding,
homogenization, or blending. The method of reducing particle size to less than 1 mm is
matrix dependent.
12.1.6.10 In general, hard particles can be reduced by grinding with a mortar and pestle. Softer
particles can be reduced by grinding in a Wiley mill or meat grinder, by homogenization,
or by blending.
12.1.6.11 The grinding, homogenization, or blending procedures should be carried out in a glove
box or fume hood to prevent particles from contaminating the work environment.
12.1.6.12 Tissue samples, certain papers and pulps, slurries and amorphous solids can be ground in
a Wiley mill or heavy-duty meat grinder. In some cases, reducing the temperature of the
sample to freezing or to dry ice or liquid nitrogen temperatures can aid in the grinding
process.
12.1.7 Preparation of Solid Samples by ASE (Optional)
12.1.7.1 Attach and tighten bottom cap onto ASE extraction cell, and insert cellulose extraction
filter. Seat filter firmly into bottom of tube. If sample appears wet add sufficient sodium
sulfate to the 10 g dry weight sample aliquot to make it free flowing. Add the sample
into extraction cell. If the sample appears oily, check with the client to confirm using a
smaller sample size of 1-3 grams.
12.1.7.2 Spike the sample aliquot with 1 mL the Labeled Toxics/LOC/window defining standard
spiking solution.
12.1.7.3 For each sample or sample set (up to 20) to be extracted in the same twelve-hour shift,
weigh two 10 g aliquots of clean sand and place each aliquot into an extraction vessel. If
an additional OPR is requested, include an additional aliquot of reference matrix material.
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12.1.7.4 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). Place the appropriate weight of client-supplied duplicate samples into
clean beakers or glass jars.
12.1.7.5 Spike one reference sample with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution. This aliquot will serve as the method blank.
12.1.7.6 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution.
This (they) will serve as the OPR spike(s).
12.1.7.7 Spike the client-supplied duplicate samples with 1 mL of the Labeled
Toxics/LOC/window defining standard spiking solution and 1 mL of the Native
Toxics/LOC standard spiking solution. These samples will serve as the matrix
spike/matrix spike duplicate set (if required).
12.1.7.8 Place loaded ASE cells into slots in the top tray of the ASE. Place labeled 60 mL vials
with septa caps into the corresponding slots in the bottom tray. UNLOCK TRAYS AND
TURN NITROGEN SUPPLY ON BEFORE ATTEMPTING TO MOVE TRAYS! Only
label the vials in the area shown on the diagram in the ASE operator's manual.
12.1.7.9 Verify that the rinse vials are not full, the solvent waste vial is not full, and the solvent
reservoir has sufficient solvent mixture for the sample set that is to be run. Check that
there is sufficient Nitrogen pressure for the entire run, also. Load the correct method into
the ASE, and run a few rinse cycles to ensure a clean system. Press the start button to
begin the run.
12.1.7.10 After the ASE has completed the sample extractions, unlock the trays and remove the
vials for spiking with surrogate and clean-up steps. Remove the cells and disassemble
them. CELLS WILL BE VERY HOT WHEN THEY COME OUT OF THE OVEN!
Send the tubes and caps to the dish room for cleaning, and sonicate the frits, PEEK seals,
thread inserts, and snap rings in toluene. Re-assemble cells when parts are cleaned and
rinsed and store with the caps on the tubes to prevent thread damage.
12.1.8 Preparation of Soil/Solid Samples by Soxhlet or MAE
12.1.8.1 Weigh a 10-gram aliquot (dry weight) of the homogenized sample, place into a Soxhlet
thimble and cover with glass wool and sand. If the sample material is wet, dry it by mixing
with extracted anhydrous sodium sulfate until free flowing before adding to the Soxhlet
thimble. Mix sample and sand well. If the sample will be extracted using Soxhlet Dean-
Stark apparatus (with toluene), no sodium sulfate should be added.
12.1.8.2 Spike the sample aliquot with 1 mL of the Labeled Toxics/LOC/window defining standard
spiking solution.
12.1.8.3 For each sample or sample set (up to 20) to be extracted in the same twelve-hour shift,
weigh two 10 g aliquots of clean sand and place each aliquot into a Soxhlet thimble. If an
additional OPR is requested, include an additional aliquot of reference matrix material.
12.1.8.4 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). Place the appropriate weight of client-supplied duplicate samples into
clean beakers or glass jars.
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12.1.8.5 Spike one reference sample with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution. This aliquot will serve as the method blank.
12.1.8.6 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining standard
spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution. This (they)
will serve as the OPR spike(s).
12.1.8.7 Spike the client-supplied duplicate samples with 1 mL of the Labeled
Toxics/LOC/window defining standard spiking solution and 1 mL of the Native
Toxics/LOC standard spiking solution. These samples will serve as the matrix
spike/matrix spike duplicate set (if required).
12.1.8.8 Prior to spiking, samples with particle size greater than 1 mm are subjected to grinding,
homogenization, or blending. The method of reducing particle size to less than 1 mm is
matrix dependent.
12.1.8.9 In general, hard particles can be reduced by grinding with a mortar and pestle. Softer
particles can be reduced by grinding in a Wiley mill or meat grinder, by homogenization,
or by blending.
12.1.8.10 The grinding, homogenization, or blending procedures should be carried out in a glove
box or fume hood to prevent particles from contaminating the work environment.
12.1.8.11 Tissue samples, certain papers and pulps, slurries and amorphous solids can be ground in
a Wiley mill or heavy duty meat grinder. In some cases, reducing the temperature of the
sample to freezing or to dry ice or liquid nitrogen temperatures can aid in the grinding
process.
12.1.9 Preparation of Milk and Milk Product Samples
12.1.9.1 Accurately measure a 100 mL aliquot of milk and transfer to a 2-liter separatory funnel.
12.1.9.2 Spike the sample aliquot with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution.
12.1.9.3 For each sample or sample set (up to 20) to be extracted in the same eight hour shift,
measure two 100 mL aliquots of de-ionized water into clean separatory funnels. If an
additional OPR is requested, include an additional aliquot of the reference matrix
material.
12.1.9.4 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20 samples). Place the appropriate weight of client-supplied duplicate samples into 2
Liter separatory funnels.
12.1.9.5 Spike one reference matrix material with 1 mL of the Labeled Toxics/LOC/window
defining standard spiking solution. This aliquot will serve as the method blank.
12.1.9.6 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution.
This (they) will serve as the OPR spike(s).
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12.1.9.7 Spike the client-supplied duplicate samples with 1 mL of the Labeled
Toxics/LOC/window defining standard spiking solution and 1 mL of the Native
Toxics/LOC standard spiking solution. These samples will serve as the matrix
spike/matrix spike duplicate set (if required).
12. Preparation of Tissue Samples
12.1.10.1 If the sample is supplied as whole fish or fillets, grind the sample using a meat grinder or
blender. Homogenize the portions of the fish requested by the client. Archive 4-8
ounces of the homogenized material in case additional testing is required. Discard the
remainder.
12.1.10.2 Weigh a 10-gram aliquot of the homogenized sample into a clean beaker. Mix in enough
extracted anhydrous sodium sulfate to dry the sample (usually approximately 20-40
grams) and allow to equilibrate. If the sample will be extracted using Soxhlet Dean-Stark
apparatus (with toluene), no sodium sulfate should be added.
12.1.10.3 Quantitatively transfer the sample into a clean Soxhlet thimble and top with extracted
glass wool.
12.1.10.4 Spike the sample aliquot with the Labeled Toxics/LOC/window defining standard spiking
solution.
12.1.10.5 For each sample or sample set (up to 20) to be extracted in the same twelve-hour shift,
weigh two 10 g aliquots of corn oil solution and place each aliquot into a Soxhlet
thimble. If an additional OPR is requested, include an additional aliquot of reference
matrix material.
12.1.10.6 A matrix spike and matrix spike duplicate may be extracted along with the sample set (up
to 20). Place the appropriate weight of client-supplied duplicate samples into Soxhlet
thimbles
12.1.10.7 Spike one reference sample with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution. This aliquot will serve as the method blank.
12.1.10.8 Spike the other aliquot(s) with 1 mL of the Labeled Toxics/LOC/window defining
standard spiking solution and 1 mL of the Native Toxics/LOC standard spiking solution.
This (they) will serve as the OPR spike(s).
12.1.10.9 Spike the client-supplied duplicate samples with 1 mL of the Labeled
Toxics/LOC/window defining standard spiking solution and 1 mL of the Native
Toxics/LOC standard spiking solution. These samples will serve as the matrix
spike/matrix spike duplicate set (if required).
12.1.10.10 Store any remaining sample in the freezer at <-10°C.
12.1.10.11 If the sample will be extracted using Soxhlet Dean-Stark apparatus (with toluene), no
sodium sulfate should be added.
12.2 SAMPLE EXTRACTION
12.2.1 Filtrates
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12.2.1.1 Quantitatively transfer the filtrate into a separatory funnel with three 20 mL rinses of
McC12.
12.2.1.2Extract by shaking the separatory funnel, venting any back pressure.
12.2.1.3 If an emulsion layer forms, allow it to dissipate, or use mechanical or chemical (salt, heat
,etc.) means to break the emulsion. Once the emulsion is broken, continue the extraction.
12.2.1.4 After the extraction allow the layers to separate.
12.2.1.5 Remove the methylene chloride layer. Repeat the extraction two times with fresh 60 mL
aliquots of methylene chloride, combining the three solvent portions.
12.2.1.6 Transfer the methylene chloride through a 10 cm plug of sodium sulfate and glass wool to a
pre-extracted Kuderna Danish concentrator. Set aside for addition of filter and particulate
extract (if applicable) or concentrate to approximately 1 mL using KD and N-evap
apparatus and proceed with sample cleanup.
12.2.2 Sludge or Samples with >1% solids
12.2.2.1 Load the wet sample aliquot into the thimble and mix with enough anhydrous sodium
sulfate to dry the sample. Use a similar approach for the filter and particulate sample from
a filtered sample aliquot. Alternatively, the extraction can be completed by substituting
sand for the sodium sulfate and fitting the Soxhlet with Dean-Stark apparatus.
12.2.2.2 Place the thimble into the toluene charged (300 mL) Soxhlet apparatus.
12.2.2.3 Add any non-aqueous liquid from the multiphase samples to the Soxhlet thimble and cover
the thimble with glass wool.
12.2.2.4 Extract the sample:
12.2.2.4.1 If necessary, adjust the reflux rate to match the rate of percolation through the
sand and silica beds until water removal lessens the restriction of toluene flow.
Check the apparatus for foaming frequently during the first two hours of
extraction. If foaming occurs, reduce the reflux rate until foaming subsides.
12.2.2.4.2 If applicable, drain the water from the receiver at 1-2 hours and 8-9 hours, or
sooner if the receiver fills with water. Reflux the sample for a minimum of 16
hours. Cool and disassemble the apparatus.
12.2.2.4.3 Remove the distilling flask, rinse the receiver with small portions of toluene and
add to the flask.
12.2.2.4.4 Cool and place a pre-rinsed Snyder column on the 500 mL round bottom flask for
concentration. The extract can otherwise be quantitatively transferred to a K-D
flask and concentrated on a steam bath.
12.2.2.4.5 Concentrate to approximately 10 mL. Remove and allow to cool for 5 minutes.
12.2.2.4.6 Rinse Snyder column down into the flask with three 2 mL portions of hexane.
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12.2.2.4.7 If, based on the appearance (cloudy or emulsive) or color (not clear) of the
extract, the extract requires acid washes, combine with the filtrate extract in a
500 mL separatory funnel or a 40 mL vial. Rinse the flask and KD with hexane
(3 x 30 mL) and add to the separatory funnel. Proceed to sample cleanup.
12.2.2.4.8 If acid washes are not required, transfer the extract through a drying column
containing a 10 cm plug of glass wool and sodium sulfate, and combine with the
filtrate portion of the extract (if applicable). Rinse the flask with hexane (3 x 30
mL) and add to the drying column. Concentrate to 1 mL using KD and N-evap
apparatus and proceed with sample cleanup.
12.2.3 Filters and Filter Particulate
12.2.3.1 Mix the filter and particulate with anhydrous sodium sulfate and load into the thimble,
add a fresh charge of toluene (300 mL) to the Soxhlet apparatus. Alternatively, the
extraction can be completed by substituting sand for the sodium sulfate and fitting the
Soxhlet with Dean-Stark apparatus.
12.2.3.2 Add any non-aqueous liquid from the multiphase samples to the Soxhlet thimble and
cover the thimble with glass wool.
12.2.3.3 Extract the sample:
12.2.3.3.1 If necessary, adjust the reflux rate to match the rate of percolation through the sand
and silica beds until water removal lessens the restriction of toluene flow. Check the
apparatus for foaming frequently during the first two hours of extraction. If foaming
occurs, reduce the reflux rate until foaming subsides.
12.2.3.3.2 If applicable, drain the water from the receiver at 1-2 hours and 8-9 hours, or sooner
if the receiver fills with water. Reflux the sample for a minimum of 16 hours. Cool
and disassemble the apparatus.
12.2.3.4 Remove the distilling flask and rinse the receiver with small portions of toluene and add to
the flask.
12.2.3.5 Cool and place a pre-rinsed Snyder column on the 500 mL round bottom flask for
concentration. The extract can otherwise be quantitatively transferred to a K-D flask and
concentrated on a steam bath.
12.2.3.5.1 Concentrate to approximately 10 mL. Remove and allow cooling for 5 minutes.
12.2.3.5.2Rinse Snyder column down into the flask with three 2 mL portions of hexane.
12.2.3.6 If, based on the appearance (cloudy or emulsive) or color (not clear) of the extract, the
extract requires acid washes, combine with the filtrate in a 500 mL separatory funnel or a
40 mL vial. Rinse the flask and KD with hexane (3 x 30 mL) and add to the separatory
funnel. Proceed to sample cleanup.
12.2.3.7If acid washes are not required, transfer the extract through a drying column containing a 10
cm plug of glass wool and sodium sulfate, and combine with the filtrate portion of the extract
(if applicable). Rinse the flask with hexane (3 x 30 mL) and add to the drying column.
Concentrate to 1 mL using KD and N-evap apparatus and proceed with sample cleanup.
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12.2.4 Soil/Solid Samples
12.2.4.1 Place the prepared sample in the thimble into the Soxhlet extractor. The Dean-Stark
attachments maybe utilized in place of the sodium sulfate drying step.
12.2.4.2 Add 300 mL of toluene and reflux for a minimum of 16 hours. Cycle at a rate of three
cycles per hour. If applicable, drain the water from the receiver as needed.
12.2.4.3 Cool and place a pre-rinsed Snyder column on the 500 mL round bottom flask for
concentration. The extract can otherwise be quantitatively transferred to a K-D flask and
concentrated on a steam bath.
12.2.4.4 Concentrate to approximately 10 mL. Remove and allow to cool for 5 minutes.
12.2.4.5 Rinse Snyder column down into the flask with three 2 mL portions of hexane.
12.2.4.6 If, based on the appearance (cloudy or emulsive) or color (not clear) of the extract, the
extract requires acid washes, transfer the extract to a 500 mL separatory funnel or a 40 mL
vial. Rinse the flask and KD with hexane (3 x 30 mL) and add to the separatory funnel.
Proceed to sample cleanup.
12.2.4.7 If acid washes are not required, transfer the extract through a drying column containing a 10
cm plug of glass wool and sodium sulfate, and combine with the filtrate portion of the extract
(if applicable). Rinse the flask with hexane (3 x 30 mL) and add to the drying column.
Concentrate to 1 mL using KD and N-evap apparatus and proceed with sample cleanup.
12.2.4.8 Solids, Filters, Sludge or Samples with >1% solids (MAE)
12.2.4.8.1 Add 50 ml of toluene to the reference cell with spiked sample. Note: Alternate
extraction solvents may be used pending method development studies.
Recondition the reference cell cover with the tool provided and then apply the
cover onto the cell. Add the reference cell to a reactor holster. Remove the TFM
sealing valve from the safety valve (cap) by unscrewing it. Remove the protection
foil from the safety valve (cap). Slide the thermo well through the opening in the
center of the protection foil and move the foil to the top of the thermo well.
Introduce the thermo well into the cell cover. The top of the thermo well should sit
flush with the cell cover. Hand-tighten the safety valve (cap) onto the reactor
holster making sure the fit is snug.
12.2.4.8.2 Add 50 ml of toluene to the other cells containing spiked samples. Note: Alternate
extraction solvents may be used pending method development studies.
Recondition the cell caps with the tool provided and then apply each cap onto the
cell. Add each cell to a reactor holster. Make sure that the TFM sealing valve is in
tightly screwed into place over a clean undamaged protection foil. Hand-tighten
the safety valve (cap) onto the reactor holster making sure the fit is snug.
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12.2.4.8.3 Plug in the temperature probe to the microwave unit and snake the probe through
the port at the top of the unit. The shrink-wrapped black tubing along the length of
the probe should fit into the split conical polypropylene piece. This split conical
piece should fit into the port at the top of the unit. Introduce the probe to the
reference rotor fitting the PEEK knob at the top of the fiber optic body snugly into
the opening on the top of the reference safety valve (cap). Place the sealed
reference reactor connected to the temperature probe into port 1 of the rotor body.
12.2.4.8.4 Add the remaining sealed reactors to the rotor body in a manner where the vent
ports on the safety valve are facing away from the other reactors. Apply the rotor
body top over the cells making sure it fits securely. Close and lock unit door.
12.2.4.8.5 Turn the unit power on and make sure that the vents are switched to the on
position. Choose the appropriate extraction profile using the touch screen unit.
Profile should operate under the following conditions:
10 min ramp time, 115° C, IOOOW
45 min extraction time, 115° C, I OOOW
5 min cool time, 0° C, OW
10 min vent
Note: These conditions can be further optimized through method development testing.
12.2.4.8.6 Ensure that twist function is activated, QP is set to 100%, and verify that the rotor
will twist in with normal motion without kinking or tangling the temperature probe.
Ensure that starting QP reading is below 20%. If above 20% additional venting of
unit may be necessary. Push start and begin extraction. Record extraction
temperature-time profile in a logbook.
12.2.4.8.7 After venting allow reactors to cool to room temperature. Use pressure relief pin
on each reactor and remove safety valves (caps) and cell covers. Decant and filter
solvent into a round bottom flask. Rinse each cell 3 times with 15 ml's of hexane
and pour rinsate through filtrate and into the round bottom flask. Using snyder
columns concentrate extract to approximately 5 ml. Rinse Snyder column down
into the flask with three 2 mL portions of hexane. Note: Concentration step can be
further optimized through method development testing.
12.2.4.8.8 Transfer each concentrated extract into a 40 ml vial. Rinse the round bottom flask
with approximately 5 ml of hexane and transfer the rinsate into the 40 ml vial.
Repeat the rinse and transfer step two additional times. Proceed to extract
enrichment.
12.2.4.8.9 If, based on the appearance (cloudy or emulsive) or color (not clear) of the extract,
the extract requires acid washes, transfer the extract to a 500 mL separatory funnel
or a 40 mL vial. Rinse the flask and KD with hexane (3 x 30 mL) and add to the
separatory funnel. Proceed to sample cleanup.
12.2.4.8.10 If acid washes are not required, transfer the extract through a drying column
containing a 10 cm plug of glass wool and sodium sulfate, and combine with the
filtrate portion of the extract (if applicable). Rinse the flask with hexane (3 x 30
mL) and add to the drying column. Concentrate to 1 mL using KD and N-evap
apparatus and proceed with sample cleanup.
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12.2.5 Water Samples
12.2.5.1 Add 100 mL of methylene chloride to the sample bottle, cap and shake for 60 seconds to
rinse the inner surface. Transfer the solvent to the separatory funnel containing the sample
and shake vigorously for two minutes, with frequent venting.
12.2.5.2 Allow the phases to separate for 10 minutes. If the emulsion between layers is greater than
one-third of the volume, apply mechanical techniques to complete separation.
12.2.5.3 Pass the solvent layer through glass chromatography drying column that contains a pre-
rinsed glass wool plug and 5 g of anhydrous sodium sulfate into a K-D flask.
12.2.5.4 Repeat the extraction twice more with fresh 100mL portions of methylene chloride and
transfer as described above. Discard the water down the drain, flushing with running water,
12.2.5.5 Rinse empty separatory funnel three times with fresh 20 mL aliquots of methylene chloride
and pass each aliquot through the column. Combine the extracts and rinsates into the K-D
flask.
12.2.5.6 Add a pre-rinsed boiling bead and concentrate on steam bath to between 5 and 10 mL. DO
NOT CONCENTRATE TO DRYNESS. Allow to cool 10 minutes.
12.2.5.7 Rinse the Snyder column and KD twice with 5 mL portions of hexane and concentrate to 1
mL on the N-evap.
12.2.5.8 Determine the original sample volume by weighing the sample bottle before and after
extraction, and by filling the sample bottle with water to the mark. Record weight to the
nearest 5 mL.
12.2.5.8.1 Proceed to the sample cleanup steps.
12.2.6 Milk and Milk Product Samples
12.2.6.1 Add 300 mL of 1.5M potassium oxalate solution and 600 mL of de-ionized water to each
sample in the separatory funnel.
12.2.6.2 Gently shake the separatory funnel for 8-10 minutes.
12.2.6.3 Add 150 mL of 1:1:1 ethanol/ether/hexane to the sample and shake gently for 3-4 minutes.
12.2.6.4 Allow the layers to separate 15-20 minutes.
12.2.6.5 Collect the milk (bottom layer) and emulsion layers in a clean 2 L beaker. (The emulsion
layer can be reduced by adding small volumes (10-30 mL) of the 1:1:1 solvent mixture to the
separatory funnel after separation of the layers.)
12.2.6.6 Transfer the clear organic layer directly to a Kuderna-Danish concentrator and set aside.
12.2.6.7 Transfer the milk and emulsion back to the separatory funnel and repeat the extraction two
more times. Combine the organic layers to the K-D flask and save the emulsion layer in a
500 mL separatory funnel.
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12.2.6.8 After the final extraction, rinse the 2 L separatory funnel with 60 mL of the 1:1:1 solvent
mixture and add to the K-D flask.
12.2.6.9 Concentrate the extract to 2 mL and allow to cool.
12.2.6.10 Quantitatively transfer the extract into the separatory funnel containing the emulsion and
add 80 mL hexane.
12.2.6.11 Perform the acid washes and cleanup as described. For milk samples, acid cleanup is not
considered optional.
NOTE: The first acid wash should not be shaken. Slowly pour the first 50 mL of
sulfuric acid into the separatory funnel and allow to separate for 15 minutes. Drain the
acid and perform the remaining washes in the normal manner.
12.2.7 Tissue Samples
12.2.7.1 Place the loaded thimble into the Soxhlet apparatus.
12.2.7.2 Add 250 mL of hexane/methylene chloride (1:1 v/v) and reflux for a minimum of 16 hours.
12.2.7.3 Cool and place a pre-rinsed Snyder column on the 500 mL round bottom flask for
concentration. The extract can otherwise be quantitatively transferred to a K-D flask and
concentrated on a steam bath.
12.2.7.4 Concentrate to approximately 10 mL. Remove and allow to cool for 5 minutes.
12.2.7.5 Rinse Snyder column down into the flask with three 2 mL portions of hexane.
12.2.7.6 Perform the acid washes and cleanup as described. For tissue samples, acid cleanup is not
considered optional.
NOTE: The first acid wash should not be shaken. Slowly pour the first 50 mL of sulfuric
acid into the separatory funnel and allow to separate for 15 minutes. Drain the acid and
perform the remaining washes in the normal manner.
12.2.7.7 If acid washes are not required, transfer the extract through a drying column containing a 10
cm plug of glass wool and sodium sulfate, and combine with the filtrate portion of the extract
(if applicable). Rinse the flask with hexane (3 x 30 mL) and add to the drying column.
Concentrate to 1 mL using KD and N-evap apparatus and proceed with sample cleanup.
12.2.7.8 Alternatively, the sample can be extracted using Soxhlet Dean-Stark apparatus and toluene.
No sodium sulfate is used with this option.
12.2.7.9 If requested, percent lipid determinations are performed on a separate aliquot of the sample
material following SOP MN-H-004 or equivalent replacement.
12.2.8 Oil Samples
12.2.8.1 Oil samples are not extracted. The samples are processed directly through extract
enrichment procedures in section 12.3
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12.3 Extract Enrichment
12.3.1 Back Extraction with Acid - Microscale
NOTE: This enrichment step is optional. It is used on extracts based on appearance and color.
If the extract is cloudy, emulisive, or multi-layered, this back extraction is employed. It is also
used when the extract is not clear or if the sample appears particularly dirty (i.e. multi-layer,
sludge-like) or contains various organic materials (i.e. milk, fish, vegetation, etc.). Most samples
undergo this procedure.
12.3.1.1 Quantitatively transfer H2O and soxhlet extracts with 15 mL of hexane to 40 mL
vials. Extracts obtained using the ASE method should be concentrated to almost dryness (-1mL)
and 15 mL of hexane added.
12.3.1.2 Partition the extract against 2-3 mL concentrated sulfuric acid. Shake for two
minutes with periodic venting into a hood. Remove and discard the acidic bottom
layer. Emulsions may be broken down by mechanical or chemical means.
12.3.1.2 Repeat 12.3.1.2, the acid washing, until no color is visible in the aqueous layer, to a
maximum of four washings.
12.3.1.3 Acid waste is collected, and then stored in labeled containers for disposal. Use
caution when handling.
12.3.1.4 Repeat step 12.3.1.2, but substitute buffer solution (100 mL 0.5 M KHZPO4 and 31
mL of 1M NaOH).
12.3.1.5 Repeat the buffer washing until the total number equals total number of acid
washing.
12.3.1.6 Concentrate extacts to approximately 1 mL on the N-evap and proceed with column
cleanup. DO NOT ALLOW THE EXTRACTS TO GO TO DRYNESS!
12.3.2 Back Extraction with Acid - Macroscale
NOTE: This enrichment step is optional. It is used on extracts based on appearance and color. of
the extract is cloudy, emulsive, or multi-layered, this back extraction is employed. It is also used
when the extract is not clear or if the sample appears particularly dirty (i.e. multi-layer, sludge-like)
or contains various organic materials (i.e. milk, fish, vegetation, etc.). If back extraction is not
performed, ensure that the samples are spiked with 1 mL of the Labeled cleanup standard spiking
solution prior to column chromatography.
12.3.2.1 Spike the separatory funnel with 1 mL of the Labeled cleanup standard spiking solution if
not already added.
12.3.2.2 Quantitatively transfer and partition the extract in 50 mL concentrated sulfuric acid. Shake
for two minutes with periodic venting into a hood. Remove and discard the aqueous bottom
layer. Emulsions may be broken down by mechanical or chemical means. Repeat until no
color is visible in the aqueous layer, to a maximum of four washings.
12.3.2.3 Acid waste is collected, then stored in labeled containers for disposal. Use caution when
handling.
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12.3.2.4 Partition the extract against 50 mL of the 5%(w/v) sodium chloride solution in the same way
as with acid. Discard the aqueous layer.
12.3.2.5 Pour the extract through a drying column containing 7 to 12 cm of anhydrous sodium sulfate
and a pre-rinsed glass wool plug. Rinse the separatory funnel with three 20 mL portions of
hexane and add to the column. Collect the extract in a 500 mL KD evaporator flask.
12.3.2.6 Add 1 to 2 clean boiling chips to the receiver and attach a three ball macro Snyder column.
Preset the column by adding approximately 1 mL of hexane through the top. Place the KD
apparatus in a hot water bath so the entire lower rounded surface of the flask is bathed in
steam.
12.3.2.7 Adjust the vertical position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 minutes. At the proper rate of distillation, the balls of
the column will actively chatter but the chambers will not flood. DO NOT ALLOW THE
EXTRACT TO GO TO DRYNESS.
12.3.2.8 When the liquid has reached an apparent volume of 1 mL, remove the KD apparatus from the
steam bath and allow to drain and cool for at least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joint into the concentrator tube with 1-2 mL of hexane.
12.3.2.9 Remove the concentrator tube from the apparatus, concentrate to approximately 1 mL on the
N-evap and proceed with column cleanup.
12.3.2.10 Silica Column
12.3.2.11 Vertically clamp a disposable glass column, 12 mm ID x 35 cm. Rinse three times with 5
mL hexane, air dry, and place a pre-extracted silanized glass wool plug into bottom.
12.3.2.12 Pack the column in the following order (bottom to top): 1 g neutral silica, 2 g basic silica, 4
g acidic silica and 2 g neutral silica. Between each layer, tap the column to settle the silica.
Wet column with 10 mL hexane after the basic silica layer is added. Plug the end of the
column with a septa when it starts dripping. Check the column for channeling. If
channeling is observed, discard the column. DO NOT allow the column to go dry.
12.3.2.13 Spike the extract with the cleanup standard, if it has not already been added.
12.3.2.14 Quantitatively transfer the sample extract onto the column using 2-2 ml rinses of hexane.
Break off the tip of the column containing the septum.
12.3.2.15 Elute the column with 90 mL hexane. Collect the eluant in a 100 mL beaker.
12.3.2.16 Dirtier samples may be processed through a larger scale version of this column. The
column is prepared as above except using a 15 mm ID column packed with (bottom to top):
I g silica gel, 4 g basic silica gel, l g silica gel, 8 g acid silica gel, 2 g silica gel and 4 g
granular anhydrous sodium sulfate. This column is washed with 50 mL hexane and eluted
with 200 mL hexane. Larger scale silica columns may also be used so long as sufficient
hexane is used to elute all PCB isomers.
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12.3.2.17 Oil samples are typically diluted IOx in hexane and are processed through a silica column
prepared in a modified TurboVap concentrator tube (the nipple has been snapped off).
Prepare as above, except layer using 10 g silica gel, 10 g basic silica gel, 10 g silica gel, 50
g acidic silica gel, 10 g silica gel and 10 g sodium sulfate. This column is washed with 50
mL hexane and eluted with 300 mL hexane. Especially dark samples can be processed
through a column using 1.5X the amounts indicated and elute with 350 mL hexane.
12.3.2.18 Concentrate the extract to approximately 1 mL using KD, N-evap apparatus or ambient air
conditions if further cleanup is required. Otherwise, proceed to final transfer, as described
below. Note: Most samples are cleaned up using only acid washes and the multi-layer
silica column.
12.3.2.19 An equivalent silica column may be substituted so long as the data meet method
requirements.
12.3.2.20 Problematic matrices (i.e., adipose tissue, waste samples, etc.) may be processed by mixing
up to 100 grams of acid silica into the sample extract. The extract should then be processed
through the above silica column.
12.3.3 Florisil Column (Optional)
12.3.3.1 Prepare a column (same dimension as alumina column) by inserting a silanized, pre-
extracted glass wool plug. Add 1.5 g of activated Florisil topped with a 1 cm layer of
anhydrous sodium sulfate.
12.3.3.2 Pre-elute the column with 20 mL of methylene chloride, followed by 10 mL of hexane.
Discard eluants.
12.3.3.3 Quantitatively transfer the extract to the top of the column with 2 mL of hexane.
12.3.3.4 Elute the column with 100 mL of ether:hexane (6% v/v) in hexane. Collect this fraction
in a pre-rinsed 100 mL beaker. Concentrate under a gentle stream of nitrogen to less than
5 mL. Proceed to final extraction preparation.
12.4 Final Extract Preparation
12.4.1 Extract Transfer
12.4.1.1 Concentrate the extract under a gentle stream of nitrogen to a volume of less than 1 mL.
Do NOT blow the sample so the portions of the solvent "ride" up the sides of the glass
vial.
12.4.1.2 Add 10 µL of nonane to an autosampler vial to act as a keeper solvent. A volume of 40
µL of nonane may otherwise be used for the keeper solvent to help achieve good
recoveries of low boiling analytes.
12.4.1.3 Quantitatively transfer the extract to the autosampler vial. Rinse the original vial with
less than 1 mL of methylene chloride/hexane (60:40 V:V). Transfer rinsate to the
autosampler vial. Repeat rinse of the autosampler vial with two additional aliquots (<1
mL) of methylene chloride. Then blow down the extract to the level of the keeper
solvent.
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12.4.1.4 Add the 10 µL of recovery standard to the extract and cap. Vortex each sample vial.
12.4.1.5 Transfer the extracts to the analytical laboratory for analysis. Extracts should be stored in
the dark at < -10°C.
12.5 Instrument Maintenance
12.5.1 There is no set schedule for the maintenance listed in this section. It is performed on anas
needed basis. Regular preventative maintenance is performed by Pace Analytical's service
engineer.
12.5.2 The rough pump oil should be changed if the pump fails to produce a vacuum lower than 10-'
mbar or if the pump oil becomes excessively dark. To do so, turn off the ion gauge, isolate and
turn off the diffusion pump and allow it to cool. When the diffusion pump is cool, isolate and
turn off the rough pump. Now drain the oil into a waste container and recap the drain. Add oil
up to the full line and turn on the pump. When the gurgling sound stops, open the valve to pump
on the instrument. After several minutes, turn on the diffusion pump. Wait another 30-45
minutes and turn on the ion gauge. Repeat at 15 minute intervals as needed to activate the gauge.
If it is a source linked pump, the source will need to be evacuated.
12.5.3 When the carrier gas, helium, pressure gets below 500 psi, the tank should be replaced.
12.5.4 The chromatographic column used for these analyses is the SPB Octyl in a 30 meter length. As
with any column, these will degrade in time. Once this degradation reaches the point where EPA
Method 1668A criteria are not met, the column needs to be replaced. Note: The column is very
susceptible to damage by oxygen. Care should be taken to ensure column temperatures are
reduced when performing any GC or injector maintenance procedures.
12.5.5 GC septa should be changed daily, batch inlet septa should be changed weekly.
12.6 Sample Analysis
12.6.1 After calibration and column performance have been established, (per Quality Control Section
Guidelines) any spikes are typically analyzed. A blank must be analyzed between calibration
standards and client samples. Introduce PFK into the batch inlet and tune the instrument to a
resolution of 10,000 (M/AM, 10% valley) using a PFK peak within the analysis mass range
(Typically m/z 331).
12.6.2 Typical Operating conditions include:
Trap current: 500 pA
Electron Energy: 32 ± 5 eV
Source Temperature: 280 °C
Emission/Trap Ratio: < 3
Accelerating Voltage: 8000 eV
12.7 Data Processing
12.7.1 The raw data files are imported into the AutoPro data processing program for integration.
Information on how to use AutoPro is available in the AutoPro manual that can be accessed on
the HRMS group computers.
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12.7.2 Calibration analyses are used both to determine response factors and to set retention time criteria.
These criteria must be met before sample analyses are performed.
12.8 CALCULATIONS
12.8.1 The PCB isomers (native or labeled) are quantified by comparison of their responses to those of
the corresponding/appropriate labeled standard. Relative response factors are calculated from
analyses of standard mixtures containing representatives of each of the PCB congener classes at
five concentration levels, and each of the internal and recovery standards at one concentration
level. The PCB response factors are calculated by comparing the sum of the responses from the
two ion masses monitored for each chlorine congener class to the sum of the responses from the
two ion masses of the corresponding isotopically labeled standard. The formula for the response
factor calculation is:
Rf = Aa x s
As x Qa
where:
Rf = Response factor
Aa = Sum of integrated areas for analyte
Qs = Quantity of labeled standard
As = Sum of integrated areas for labeled standard
Qa = Quantity of analyte
12.8.2 The levels of PCBs in the samples are quantified using the following equation:
C= Anx is
AisxWxRf
where:
C = Concentration of target isomer
An = Sum of integrated areas for the target isomer
Qis = Quantity of labeled internal standard added to the sample
Ais = Sum of integrated areas for the labeled internal standard
W = Sample amount
Rf = Response factor
12.8.3 A method detection limit (MDL), based on the signal to noise ratio of the noise level of the ion of
interest versus the appropriate standard, may be calculated for each sample and isomer. The
equation used for calculating the MDL is:
MDL=HnxQis x2.5
HisxWxRf
where:
MDL = Method Detection Limit
Hn = Sum of noise heights for target isomer
Qis = Quantity of labeled internal standard added to the sample
His = Sum of signal heights from labeled internal standard
W = Sample amount
Rf = Response factor
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Note: If a signal is present which does not meet the ion ratio
requirement but is greater than 2:5:1 S/N, the 2.5 factor is omitted
for that ion mass.
12.8.4 The Estimated Method Limits (EMLs) have been set to 500 pg/sample and are used as reporting
limits provided that the signal to noise based limits, calibration range and freedom from
laboratory background levels support this limit. These levels will be reported as PRLs (Practical
Reporting Limits). Analytes in diluted extracts may be reported down to the concentration
equivalent to the low calibration point of the method (a 25x dilution).
12.8.5 The recoveries of the internal and cleanup standards are calculated using the following equation:
%R = Ais x Qrs x 100
Rfr x Ars x Qis
where:
%R = Percent recovery of labeled internal or cleanup standard
Ais = Sum of integrated areas of labeled internal or cleanup standard
Qrs = Quantity of recovery standard
Ars = Sum of integrated areas of recovery standard
Rfr = Response factor of the specific labeled internal or cleanup standard relative
13. QUALITY CONTROL
13.1 The quality of the sample processing steps and instrument performance are monitored on a routine basis.
The procedures and criteria are summarized below.
13.1.1 Internal standards are spiked into each sample prior to extraction in order to monitor the level of
recovery, which is achieved for each individual sample. Acceptable recoveries range from 25 to
150% for the internal standards unless a deviation is due to variation in instrument response as a
result of analytical interferences. Acceptable recoveries for cleanup standards range from 30 to
135%. If selected recoveries are outside the target range, the results may be discussed in the
narrative of the report or the samples may be re-analyzed after dilution or re-extraction.
13.1.2 Prior to each analysis, the resolution of the mass spectrometer is verified to be 10,000 or greater.
Due to the mass range monitored, a resolution of as low as 8,000 is acceptable so long as the
resolution at the mid point of the mass range is 10,000 or more. Hardcopies of the reference
peaks are printed at the beginning and end of each analytical shift (as staffing permits). The
resolving power of the SPB Octyl (or equivalent) chromatographic column is checked daily by
analyzing the 209-congener mix standard.
13.1.3 Initial calibrations are generated by analyzing standard solutions containing target native and
labeled PCB compounds. Response factors are calculated and averaged for each compound.
These averages are used for quantification and for comparison to the daily continuing calibration.
The relative standard deviation for each native compound must be 20% or less. A continuing
calibration standard is analyzed at the beginning of each 12-hour shift on days when initial
calibrations are not performed. The initial calibration is considered to be valid when the native
analyte response factors from the continuing calibration analysis agree to within ± 30% (50% for
internal standards, -40% to +30% for cleanup standards) of the average from the initial
calibration. The response factors for analytes not included in the continuing calibration solution
are determined daily by the analysis of the diluted 209 congener solution.
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13.2 Samples are queued as discussed in the data processing section of this SOP. In order for a peak to be
accepted as a PCB isomer, the following criteria must be met:
13.2.1 Isotope ratios must be within 15% of the corresponding standard.
13.2.2 The signal to noise of the peak versus the background noise must be >2.5:1 (10:1 for calibration
standards).
13.2.3 The peak elutes within the retention time determined from the analysis of the column
performance window mix standard.
13.3 Data Acceptance/Rejection Criteria and Corrective Action
13.3. Extraction Corrective Action
13.3.1.1 If a laboratory error occurs during the extraction process that results in the loss of an extract
prior to final concentration and transfer of the sample, a new aliquot may be re-extracted
and added to the original batch. The new aliquot must be set up within 24 hours for the set
up of the first sample in the extraction batch or it must be put into a new batch. This may
include a QC aliquot.
13.3.1.2 Make note of any error and corrective action on the extraction sheet. Include times of
laboratory error and re-set up of the aliquot.
13.3.2 Method Blank
13.3.2.1 One method blank is typically prepared with each twenty samples of any given matrix.
13.3.2.2 A method blank or solvent blank must be analyzed between standards and samples to
demonstrate lack of PCB carryover.
13.3.2.3 If the blank contains PCBs within the reporting range for the method, find and correct the
source of the problem.
13.3.2.3.1 If the contamination appears to be instrument related, correct the problem, analyze a
solvent blank, and reanalyze the method blank before proceeding with samples.
13.3.2.3.2 If the contamination appears to be from the extraction or enrichment steps, the
analysis of samples may continue. If the sample shows similar contamination that
could potentially bias the sample results (sample level < IOx blank level) it should
be re-extracted, if possible. The presence or absence of high levels of other isomers
should also be considered when determining a course of action. All associated
sample results will be qualified for blank contamination when any analyte is
detected in the method blank at 10% of more of the sample concentration.
13.3.3 Laboratory Control Spike
13.3.3.1 One laboratory control spike is prepared with each batch of 20 samples of any given
matrix. If matrix spikes are not prepared with a batch of 20 samples, a second LCS will
also be included. Acceptable recoveries of the native PCB analytes in the spiked samples
range from 50 to 150% for natives, 30 to 140% for internal standards and 40 to 125% for
cleanup standards.
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NOTE: Recoveries of up to 3 native analytes outside the acceptable range do not
invalidate the data but provide information, which is used by the laboratory to monitor
recovery trends and to assure optimization of the method. Affected data will be qualified
with a detailed explanation of data impact in the narrative section of the final report or the
samples will be re-extracted and reanalyzed.
13.3.3.2 Accuracy of the standard spiking solutions should, at a minimum, be verified semi-annually
by comparison of the solutions to certified native materials obtained from a second source
or batch.
13.3.4 Matrix Spike/Matrix Spike Duplicate
13.3.4.1 Matrix spike samples should be prepared with each batch of 20 or fewer samples. If
prepared, the recoveries of the native PCB analytes in the spiked samples should fall
within the OPR acceptance ranges if not affected by levels or interferences present in
the sample material.
NOTE: Recoveries of selected analytes outside the acceptable range do not invalidate
the data but provide information, which is used by the laboratory to monitor recovery
trends and to assure optimization of the method. This is particularly true of MS/MSD
recoveries where native PCBs are subject to the affects of the sample source.
13.4 REPORTING AND REVIEW
13.4.1 Reports are prepared using previous reports as templates and making modification as appropriate.
The amount of information included with the report is determined based on the client
requirements.
13.4.2 Units/Significant Figures
13.4.2.1 Values within the calibration range are reported to three significant figures. Values below
the calibration range should be reported to two significant figures. Aqueous samples are
routinely reported in units of pg/L or ng/L and solid matrices are reported in ng/Kg. Other
matrices are reported in units specific to instrument sensitivity and extraction capability and
can be provided upon request.
13.4.3 Data Qualifiers/Flags
13.4.3.1 The information typically reported is summarized below.
13.4.3.1.1 Base Report
13.4.3.1.1.1 Case Narrative including client name, address, and project information,
introduction, sample information and discussion of results.
13.4.3.1.1.2 Copies of chain of custody documents and analytical requests.
13.4.3.1.1.3 Data summary tables (sample and QC analysis results)
13.4.3.1.2 Full Report
13.4.3.1.3 Those items listed in base report summary.
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13.4.3.1.3.1 Methodology, example calculations, QA/QC summary.
13.4.3.1.3.2 Raw data including sample, QC sample and standards.
13.4.3.1.3.3 Selected ion current profiles (chromatograms).
13.4.3.1.3.4 Communications records.
13.4.3.1.3.5 Extraction and login forms.
13.4.3.1.3.6 Instrument resolution checks.
13.4.3.1.3.7 Calibration Results.
13.4.4 Those items included in the report may be tailored to the clients requirements and may not fit into
the above stated categories.
13.4.5 Levels of Review
13.4.5.1 Each sample work-up must be rechecked for work-up and header information accuracy.
The results of this review are recorded on the raw data sheet.
13.4.5.2 All data generated during analysis are peer reviewed prior to inclusion in the final report.
The final report is reviewed by the project manager.
13.4.5.3 Initial and Continuing Calibration standard data are stored in a QA notebook located near
each instrument.
13.4.5.4 After reporting, the complete project file is archived in the chemistry archive.
14. METHOD PERFORMANCE
14.1 There are several requirements that must be met to insure that this procedure generates accurate and
reliable data. A general outline of requirements has been summarized below. Further specifications may
be found in the Laboratory Quality Manual and specific Standard Operating Procedures.
14.1.1 The analyst must read and understand this procedure with written documentation maintained
in his/her training file which is located in the QA Office.
14.1.2 An initial demonstration of capability (IDC) must be performed per SOP ALL-Q-20 or
equivalent. A record of the IDC will be maintained in his/her file with written authorization
from the Laboratory Manager and Quality Manager. Results are stored in the QA office.
14.1.3 An annual minimum detection limit (MDL) study following SOP ALL-Q-004 or equivalent
will be completed for this method and whenever there is a major change in personnel or
equipment. Results are stored in the QA Office.
14.1.4 Periodic performance evaluation (PE) samples are analyzed to demonstrate continuing
competence per SOP ALL-Q-010 or equivalent. Results are stored in the QA office.
15. POLLUTION PREVENTION AND WASTE MANAGEMENT
15.1 The quantity of chemicals purchased is based on expected usage during its shelf life and disposal cost of
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unused material. Actual reagent preparation volumes should reflect anticipated usage and reagent
stability.
15.2 The Environmental Protection Agency (USEPA) requires that laboratory waste management practice be
consistent with all applicable rules and regulations. Excess reagents, samples and method process wastes
are characterized and disposed of in an acceptable manner. For further information on waste management
consult SOP ALL-S-002, Waste Handling or equivalent replacement.
16. REFERENCES
16.1 USEPA Method 1668, Revision A: Chlorinated Biphenyl Congeners in Water, Soil, Sediment and Tissue
by HRGC/HRMS (December 1999).
17. TABLES, DIAGRAMS, FLOWCHARTS, APPENDICES, ADDENDA
17.1 Attachment # 1: PCBExtraction Worksheet
17.2 Attachment 42: Full Validation Checklist
17.3 Attachment 43: Method 1668A Tables
18. REVISIONS
Revision Change Date
MN-H-014-Rev.3 Reformatted to conform to current corporate requirements. 18-Nov-04
Definitions removed and Analytical Definitions SOP cited.
Reflux time changed from 16-18 hours to read "a minimum of 16 hours".
LCS and MS requirements clarified.
MN-H-014-Rev.5 Added method required sample preservation to section 8. 18-May-05
MN-H-014-Rev.6 10.1 Changed reverification criteria to be calibration limits. 11-Apr-06
11.1.3.1 Corrected compound.
12.6.1 - PFK for PFTBA/HA and 331 for 364
Updated Attachment #1 to current revision of form.
Labeled Tables, #1, #3, #4
MN-H-014-Rev.7 12.3 Changed to define microscale 28-Jul-06
11.2.1.3 Changed 45% to read -40% to +30%
Table 4 place A2 cont. and B2 cont. on second page.
S-M N-H-014-
Rev.08 Added Congener reference table to section 2 19Sep2007
12.1.4.3 Added "Refill with fresh extraction solvent"
Removed statements from 12.1.7.3, 12.1.8.3, 12.2.2.4.2, 12.2.3.3.2 and
12.2.4.2
Added Oil prep procedure to 12.2.8 and 12.3.2.17
Added Extraction Corrective Action to section 13
Corrected spacing and formatting
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ATTACHMENT #1: Example PCB Extraction Worksheet
DIOXIN EXTRACTION WORKSHEET
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Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 35 of 63
ATTACHMENT #2
Full Validation Package Checklist
Text
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Appendix F
Case Narrative
Tables
Chain of Custody
Copy of Airbill
"Blackout" Sheet
Extraction Sheet Copy
Moisture Sheet Copy
HRMS Logbook Page Copies
HRMS Resolution Check Copies
(If Requested)
Sample Results
Blank Results
Spike Results
MS/MSD Relative Percent
Difference Results
Calibration Results
Sample Chromatograms
Sample Raw Data
Standard Chromatograms
Standard Raw Data
Blank Chromatograms
Spike Chromatograms
Blank Raw Data
Spike Raw Data
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 36 of 63
ATTACHMENT #3: Method 1668A Tables
Table #1: Analyte List
CB congener 1 IUPAC
number CAS registry
number Labeled analog IUPAC analog CAS registry
number
2-MoCB 1 2051-60-7 1'C12-2-MoCB2 1L 234432-85-0
3-MoCB 2 2051-61-8
4-MoCB 3 2051-62-9 1'C12-4-MoCB2 3L 208263-77-8
2,2'-DiCB 4 13029-08-8 1'C12-2,2'-DiCB2 4L 234432-86-1
2,3-DiCB 5 16605-91-7
2,3'-DiCB 6 25569-80-6
2,4-DiCB' 7 32284-50-3
2,4'-DiCB 8 34883-43-7
2,5-DiCB 9 34883-39-1 1'C12-2,5-DiCB4 9L 250694-89-4
2,6-DiCB 10 33146-45-1
3,3'-DiCB 11 2050-67-1
3,4-DiCB 12 2974-92-7
3,4'-DiCB 13 2974-90-5
3,5-DiCB 14 34883-41-5
4,4'-DiCB 15 2050-68-2 1'C12-4,4'-DiCB2 15L 208263-67-6
2,2',3-TrCB 16 38444-78-9
2,2',4-TrCB 17 37680-66-3
2,2',5-TrCB' 18 37680-65-2
2,2',6-TrCB 19 38444-73-4 1'C12-2,2',6-TrCB2 19L 234432-87-2
2,3,3'-TrCB 20 38444-84-7
2,3,4-TrCB 21 55702-46-0
2,3,4'-TrCB 22 38444-85-8
2,3,5-TrCB 23 55720-44-0
2,3,6-TrCB 24 66803-45-9
2,3',4-TrCB 25 66823-37-3
2,3',5-TrCB 26 38444-81-4
2,3',6-TrCB 27 38444-76-7
2,4,4'-TrCB' 28 7012-37-5 1'C12-2,2',4-TriCB5 28L 208263-76-7
2,4,5-TrCB 29 15862-07-4
2,4,6-TrCB 30 35693-92-6
2,4',5-TrCB 31 16606-02-3
2,4',6-TrCB 32 38444-77-8
2',3,4-TrCB 33 38444-86-9
2',3,5-TrCB 34 37680-68-5
3,3',4-TrCB 35 37-680-69-6
3,3',5-TrCB 36 38444-87-0
3,4,4'-TrCB 37 38444-90-5 1'C12-3,4,4'-TrCB2 37L 208263-79-0
3,4,5-TrCB 38 53555-66-1
3,4',5-TrCB 39 38444-88-1
2,2',3,3'-TeCB 40 38444-93-8
2,2',3,4-TeCB 41 52663-59-9
2,2',3,4'-TeCB 42 36559-22-5
2,2',3,5-TeCB 43 70362-46-8
2,2',3,5'-TeCB' 44 41464-39-5
2,2',3,6-TeCB 45 70362-45-7
2,2',3,6'-TeCB 46 41464-47-5
2,2',4,4'-TeCB 47 2437-79-8
2,2',4,5-TeCB 48 70362-47-9
2,2',4,5'-TeCB 49 41464-40-8
2,2',4,6-TeCB 50 62796-65-0
2,2',4,6'-TeCB 51 68194-04-7
2,2',5,5'-TeCB' 52 35693-66-3 13C12-2,2',5,5'-TeCB4 52L 208263-80-3
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 37 of 63
2,2',5,6'-TeCB 53 41464-41-9
2,2',6,6'-TeCB 54 15986-05-5 1'C12-2,2',6,6'-TeCB2 54L 234432-88-3
2,3,3',4'-TeCB 55 74338-24-2
2,3,3',4'-TeCB 56 41464-43-1
2,3,3',5-TeCB 57 70424-67-8
2,3,3',5'-TeCB 58 41464-49-7
2,3,3',6-TeCB 59 74472-33-6
2,3,4,4'-TeCB 60 33025-41-1
2,3,4,5-TeCB 61 33284-53-6
2,3,4,6-TeCB 62 54230-22-7
2,3,4',5-TeCB 63 74472-34-7
2,3,4',6-TeCB 64 52663-58-8
2,3,5,6-TeCB 65 33284-54-7
2,3',4,4'-TeCB' 66 32598-10-0
2,3',4,5-TeCB 67 73575-53-8
2,3',4,5'-TeCB 68 73575-52-7
2,3',4,6-TeCB 69 60233-24-1
2,3',4',5-TeCB 70 32598-11-1
2,3',4',6-TeCB 71 41464-46-4
2,3',5,5'-TeCB 72 41464-42-0
2,3',5',6-TeCB 73 74338-23-1
2,4,4',5-TeCB 74 32690-93-0
2,4,4',6-TeCB 75 32598-12-2
2',3,4,5-TeCB 76 70362-48-0
3,3',4,4'-TeCB1•6 77 32598-13-3 1'C12-3,3',4,4'-TeCB2•' 77L 105600-23-5
3,3',4,5-TeCB 78 70362-49-1
3,3',4,5'-TeCB 79 41464-48-6
3,3',5,5'-TeCB 80 33284-52-5
3,4,4',5-TeCB6 81 70362-50-4 1'C12-3,4,4',5-TeCB' 81L 208461-24-9
2,2',3,3',4-PeCB 82 52663-62-4
2,2',3,3',5-PeCB 83 60145-20-2
2,2',3,3',6-PeCB 84 52663-60-2
2,2',3,4,4'-PeCB 85 65510-45-4
2,2',3,4,5-PeCB 86 55312-69-1
2,2',3,4,5'-PeCB 87 38380-02-8
2,2',3,4,6-PeCB 88 55215-17-3
2,2',3,4,6'-PeCB 89 73575-57-2
2,2',3,4',5-PeCB 90 68194-07-0
2,2',3,4',6-PeCB 91 68194-05-8
2,2',3,5,5'-PeCB 92 52663-61-3
2,2',3,5,6-PeCB 93 73575-56-1
2,2',3,5,6'-PeCB 94 73575-55-0
2,2',3,5',6-PeCB 95 38379-99-6
2,2',3,6,6'-PeCB 96 73575-54-9
2,2',3',4,5-PeCB 97 41464-51-1
2,2',3,4,6-PeCB 98 60233-25-2
2,2',4,4',5-PeCB 99 38380-01-7
2,2',4,4',6-PeCB 100 39485-83-1
2,2',4,5,5'-PeCB3 101 37680-73-2 13C12-2,2',4,4',5'-PeCB4 101L 104130-39-4
2,2',4,5,6'-PeCB 102 68194-06-9
2,2',4,5',6-PeCB 103 60145-21-3
2,2',4,6,6'-PeCB 104 56558-16-8 13C12-2,2',4,4',6,6'-PeCB2 104L 234432-89-4
2,3,3',4,4'-PeCB3,6 105 32598-14-4 13C12-2,3,3',4,4'-PeCB' 105L 208263-62-1
2,3,3',4,5-PeCB 106 70424-69-0
2,3,3',4',5-PeCB 107 70424-68-9
2,3,3',4,5'-PeCB 108 70362-41-3
2,3,3',4,6-PeCB 109 74472-35-8
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 38 of 63
2,3,3',4',6-PeCB 110 38380-03-9
2,3,3',5,5'-PeCB 111 39635-32-0 13C12-2,3,3',5,5'-PeCB? 111L 235416-29-2
2,3,3',5,6-PeCB 112 74472-36-9
2,3,3',5',6-PeCB 113 68194-10-5
2,3,4,4',5-PeCB6 114 74472-37-0 13C12-2,3,4,4',5-PeCB? 114L 208263-63-2
2,3,4,4',6-PeCB 115 74472-38-1
2,3,4,5,6-PeCB 116 18259-05-7
2,3,4',5,6-PeCB 117 68194-11-6
2,3',4,4',5-PeCB3.6 118 31508-00-6 13C12-2,3',4,4',5-PeCB? 118L 104130-40-7
2,3',4,4',6-PeCB 119 56558-17-9
2,3',4,5,5'-PeCB 120 68194-12-7
2,3',4,5',6-PeCB 121 56558-18-0
2,3,3',4,5-PeCB 122 76842-07-4
2',3,4,4',5-PeCB6 123 65510-44-3 13C12-2',3,4,4',5-PeCB? 123L 208263-64-3
2',3,4,5,5'-PeCB 124 70424-70-3
2',3,4,5,6'-PeCB 125 74472-39-2
3,3',4,4',5-PeCB3.6 126 57465-28-8 13C12-3,3',4,4',5-PeCB2•7 126L 208263-65-4
3,3',4,5,5'-PeCB 127 39635-33-1
2,2',3,3',4,4'-HxCB3 128 38380-07-3
2,2',3,3',4,5-HxCB 129 55215-18-4
2,2',3,3',4,5'-HxCB 130 52663-66-8
2,2',3,3',4,6-HxCB 131 61798-70-7
2,2',3,3',4,6'-HxCB 132 38380-05-1
2,2',3,3',5,5'-HxCB 133 35694-04-3
2,2',3,3',5,6-HxCB 134 52704-70-8
2,2',3,3',5,6'-HxCB 135 52744-13-5
2,2',3,3',6,6'-HxCB 136 38411-22-2
2,2',3,4,4',5-HxCB 137 35694-06-5
2,2',3,4,4',5'-HxCB3 138 35065-28-2 13C12-2,2',3,4,4',5'-HxCB4 138L 208263-66-5
2,2',3,4,4',6-HxCB 139 56030-56-9
2,2',3,4,4',6'-HxCB 140 59291-64-4
2,2',3,4,5,5'-HxCB 141 52712-04-6
2,2',3,4,5,6-HxCB 142 41411-61-4
2,2',3,4,5,6'-HxCB 143 68194-15-0
2,2',3,4,5',6-HxCB 144 68194-14-9
2,2',3,4,6,6'-HxCB 145 74472-40-5
2,2',3,4',5,5'-HxCB 146 51908-16-8
2,2',3,4',5,6-HxCB 147 68194-13-8
2,2',3,4',5,6'-HxCB 148 74472-41-6
2,2',3,4',5',6-HxCB 149 38380-04-0
2,2',3,4',6,6'-HxCB 150 68194-08-1
2,2',3,5,5',6-HxCB 151 52663-63-5
2,2',3,5,6,6'-HxCB 152 68194-09-2
2,2',4,4',5,5'-HxCB3 153 35065-27-1
2,2',4,4',5',6-HxCB 154 60145-22-4
2,2',4,4',6,6'-HxCB 155 33979-03-2 13C12-2,2',4,4',6,6'-HxCB2 155L 234432-90-7
2,3,3',4,4',5-HxCB6 156 38380-08-4 13C12-2,3,3',4,4',5-HxCB? 156L 208263-68-7
2,3,3',4,4',5'-HxCB6 157 69782-60-7 13C12-2,3,3',4,4',5'-HxCB? 157L 235416-30-5
2,3,3',4,4',6-HxCB 158 74472-42-7
2,3,3',4,5,5'-HxCB 159 39635-35-3
2,3,3',4,5,6-HxCB 160 41411-62-5
2,3,3',4,5',6-HxCB 161 74472-43-8
2,3,3',4',5,5'-HxCB 162 39365-34-2
2,3,3',4',5,6-HxCB 163 74472-44-9
2,3,3',4',5',6-HxCB 164 74472-45-0
2,3,3',5,5',6-HxCB 165 74472-46-1
2,3,4,4',5,6-HxCB 166 41411-63-6
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 39 of 63
2,3',4,4',5,5'-HxCB6 167 52663-72-6 13C12-2,3',4,4',5,5'-HxCB7 167L 208263-69-8
2,3',4,4',5',6-HxCB 168 59291-65-5
3,3',4,4',5,5'-HxCB3.6 169 32774-16-6 13C12-3,3',4,4',5,5'-HxCB2' 169L 208263-70-1
2,2',3,3',4,4',5-HpCB3 170 35065-30-6
2,2',3,3',4,4',6-HpCB 171 52663-71-5
2,2',3,3',4,5,5'-HpCB 172 52663-74-8
2,2',3,3',4,5,6-HpCB 173 68194-16-1
2,2',3,3',4,5,6'-HpCB 174 38411-25-5
2,2',3,3',4,5',6-HpCB 175 40186-70-7
2,2',3,3',4,6,6'-HpCB 176 52663-65-7
2,2',3,3',4',5,6-HpCB 177 52663-70-4
2,2',3,3',5,5',6-HpCB 178 52663-67-9 13C12-2,2',3,3',5,5',6-HpCB5 178L 232919-67-4
2,2',3,3',5,6,6'-HpCB 179 52663-64-6
2,2',3,4,4',5,5'-HpCB3 180 35065-29-3
2,2',3,4,4',5,6-HpCB 181 74472-47-2
2,2',3,4,4',5,6'-HpCB 182 60145-23-5
2,2',3,4,4',5',6-HpCB 183 52663-69-1
2,2',3,4,4',6,6'-HpCB 184 74472-48-3
2,2',3,4,5,5',6-HpCB 185 52712-05-7
2,2',3,4,5,6,6-HpCB 186 74472-49-4
2,2',3,4',5,5',6-HpCB3 187 52663-68-0
2,2',3,4',5,6,6'-HpCB 188 74487-85-7 13C12-2,2',3,4',5,6,6'-HpCB2 188L 234432-91-8
2,3,3',4,4',5,5'-HpCB6 189 39635-31-9 13C12-2,3,3',4,4',5,5'-HpCB2' 189L 208263-73-4
2,3,3',4,4',5,6-HpCB 190 41411-64-7
2,3,3',4,4',5',6-HpCB 191 74472-50-7
2,3,3',4,5,5',6-HpCB 192 74472-51-8
2,3,3',4',5,5',6-HpCB 193 69782-91-8
2,2',3,3',4',5,5-OcCB 194 35694-08-7 13C12-2,2',3,3',4,4',5,5'-000B4 194L 208263-74-5
2,2',3,3',4',5,6-OcCB3 195 52663-78-2
2,2',3,3',4',5,6'-OcCB 196 42740-50-1
2,2',3,3',4',6,6'-OcCB 197 33091-17-7
2,2',3,3',4',5,5',6-OcCB 198 68194-17-2
2,2',3,3',4,5,5',6'-OcCB 199 52663-75-9
2,2',3,3',4,5,6,6'-OcCB 200 52663-73-7
2,2',3,3',4,5',6,6'-OcCB 201 40186-71-8
2,2',3,3',5,5',6,6'-OcCB 202 2136-99-4 13C12-2,2',3,3',5,5',6,6'-OcCB2 202L 105600-26-8
2,2',3,4,4',5,5',6-OcCB 203 52663-76-0
2,2',3,4,4',5,6,6'-OcCB 204 74472-52-9
2,3,3',4,4',5,5',6-OcCB 205 74472-53-0 13C12-2,3,3',4,4',5,5',6-OcCB2 205L 234446-64-1
2,2',3,3',4,4',5,5',6-OcCB3 206 40186-72-9 13C12-2,2',3,3',4,4',5,5',6-NoCB2 206L 208263-75-6
2,2',3,3',4,4',5,6,6'-OcCB 207 52663-79-3
2,2',3,3',4,5,5',6,6'-OcCB 208 52663-77-1 13C12-2,2',3,3',4,5,6,6'-NoCB2 208L 234432-92-9
DeCB3 209 2051-24-3 13C12-DeCB2 209L 105600-27-9
1. Abbreviations for chlorination levles
MoCB = monochlorobiphenyl DiCB = dichlorobiphenyl TrCB = trichlorobiphenyl
TeCB = tetrachlorbiphenyl PeCB = pentachlorobiphenyl HxCB = hexachlorobiphenyl
HpCB = heptachlorobiphenyl OcCB = octachlorobiphenyl NoCB = nonachlorobiphenyl
DeCB = decachlorobiphenyl
2. Labeled level of chlorination (LOC) window defining congener 5. Labeled clean-up standard
3. Nat'l Oceanic and Atmospheric Administration (NOAA) congener of interest 6. World Health Organization (WHO) toxic congener
4. Labeled injection internal standard 7. Labeled analog of WHO toxic congener
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 40 of 63
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Pace Analytical Services, Inc. Date: Upon Final Signature
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Pace Analytical Services, Inc. Date: Upon Final Signature
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Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
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Table #3: Spike Amounts and Solution Concentrations
Solution Concentrations
CB congener Stock (tg/mL) Spiking (ng/mL) Extract (ng/mL)
Native Toxics/LOCI
1 20 1.0 50
3 20 1.0 50
4 20 1.0 50
15 20 1.0 50
19 20 1.0 50
37 20 1.0 50
54 20 1.0 50
77 20 1.0 50
81 20 1.0 50
104 20 1.0 50
105 20 1.0 50
114 20 1.0 50
118 20 1.0 50
123 20 1.0 50
126 20 1.0 50
155 20 1.0 50
156 20 1.0 50
157 20 1.0 50
167 20 1.0 50
169 20 1.0 50
188 20 1.0 50
189 20 1.0 50
202 20 1.0 50
205 20 1.0 50
206 20 1.0 50
208 20 1.0 50
209 20 1.0 50
Native congener mix stock solutions2
MoCB thru TrCB 2.5
TeCb thru HpCB 5.0
OcCB thru DeCB 7.5
Labeled Toxics/LOC/window-defining'
1L 1.0 2.0 100
3L 1.0 2.0 100
4L 1.0 2.0 100
15L 1.0 2.0 100
19L 1.0 2.0 100
37L 1.0 2.0 100
54L 1.0 2.0 100
77L 1.0 2.0 100
81L 1.0 2.0 100
104L 1.0 2.0 100
105L 1.0 2.0 100
Determination of PCBs Congeners by 1668A
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Solution Concentrations
CB congener Stock (tg/mL) Spiking (ng/mL) Extract (ng/mL)
114L 1.0 2.0 100
118L 1.0 2.0 100
123L 1.0 2.0 100
126L 1.0 2.0 100
155L 1.0 2.0 100
156L 1.0 2.0 100
157L 1.0 2.0 100
167L 1.0 2.0 100
169L 1.0 2.0 100
188L 1.0 2.0 100
189L 1.0 2.0 100
202L 1.0 2.0 100
205L 1.0 2.0 100
206L 1.0 2.0 100
208L 1.0 2.0 100
209L 1.0 2.0 100
Labeled clean-up4
28L 1.0 2.0 100
111L 1.0 2.0 100
178L 1.0 2.0 100
Labeled injection internals
9L 5.0 200 100
52L 5.0 200 100
l O 1L 5.0 200 100
138L 5.0 200 100
194L 5.0 200 100
Diluted combined 209 congener6
Solution Concentrations (µg/mL)
Standard Native Labeled
Native Congeners
MoCB thru TrCB 50
TeCB thru HpCB 100
OcCB thru DeCB 150
Labeled Toxics/LOC/window-defining 100
Labeled Cleanup 100
Labeled Injection internal 100
Stock solution: Section 7.8.1; Spiking solution: Section 7.11
Section 7.8.1.2
Stock solution: Section 7.9.1; Spiking solution: Section 7.12
Stock solution: Section 7.9.2; Spiking solution: Section 7.13
Stock solution: Section 7.9.3; Spiking solution: Section 7.14
Section 7.10.2.2.2
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 52 of 63
Table #4: Native CB Congener Stock Solution
Solution identifier
A2 B2 C2 D2 E2
Accu-Standard part number
M-1668A-1 M-1668A-2 M-1668A-3 M-1668A-4 M-1668A-5
2 7 13 25 1
10 5 17 21 3
9 12 29 69 4
6 18 20 47 15
8 24 46 42 19
14 23 65 64 16
11 28 59 70 37
30 22 40 102 54
27 39 67 97 43
32 53 76 115 44
34 51 80 123 74
26 73 93 134 56
31 48 84 131 77
33 62 101 163 104
36 71 112 180 98
38 68 86 125
35 58 116 110
50 61 109/107 126
45 55 154 155
52 60 147 138
49 94 140 169
75 100 146 188
41 91 141 189
72 121 164 202
57 90 158 205
63 99 182 208
66 108/109 174 206
79 117 173 209
78 111 193
81 107/108
96 118
103 114
95 150
88 145
89 135
92 149
113 139
83 132
119 165
87 168
85 137
82 160
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
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A2 cont. B2 cont.
120 128
124 162
106 157
122 184
105 186
127 187
152 185
136 181
148 192
151 197
144 199/201
143 203
142
133
161
153
130
129
166
159
167
156
179
176
178
175
183
177
171
172
191
170
190
201/200
204
200-199
198
196
195
194
207
Totals
83 54 29 15 28
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
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Table 5. Concentration of CB congeners in calibration and calibration verification standards
Solution concentration (ag/mL)

CB congener
IUPAC' CS-0.2
(Hi sens)2
CS-1
CS-2 CS-3
(VER)
CS4
CS-5
Native Toxics[LOC
2-MoCB 1 0.2 1.0 5.0 50 400 2000
4-MoCB 3 0.2 1.0 5.0 50 400 2000
2,2'-DiCB 4 0.2 LO 5.0 50 400 2000
4,4'-DiCB 15 0.2 LO 5.0 50 400 2000
2,2',6'-TrCB 19 0.2 LO 5.0 50 400 2000
3,4,4'-TrCB 37 0.2 LO 5.0 50 400 2000
2,2',6,6'-TeCB 54 0.2 L0 5.0 50 400 2000
3,3',4,4'-TeCB 77 0.2 1.0 5.0 50 400 2000
3,4,4',5-TeCB 81 0.2 1.0 5.0 50 400 2000
2,2',4,6,6'-PeCB 104 0.2 1.0 5.0 50 400 2000
2,3,3',4,4'-PeCB 105 0.2 1.0 5.0 50 400 2000
2,3,4,4',5-PeCB 114 0.2 1.0 5.0 50 400 2000
2,3',4,4',5-PeCB 118 0.2 1.0 5.0 50 400 2000
2',3,4,4',5-PeCB 123 02 1.0 5.0 50 400 2000
3,3',4,4',5-PeCB 126 0.2 1.0 5.0 50 400 2000
2,21,4,4',6,6'-HxCB 155 0.2 1.0 5.0 50 400 2000
2,3,3',4,4',5-HxCB 156 01 1.0 5.0 50 400 2000
2,3,3',4,4',5'-HxCB 157 0.2 1.0 5.0 50 400 2000
2,3',4,4',5,5'-HxCB 167 0.2 1.0 5.0 50 400 2000
3,3',4,4',5,5'-HxCB 169 0.2 1.0 5.0 50 400 2000
2,2',3,4',5,6,6'-HpCB 188 0.2 1.0 5.0 50 400 2000
2,3,3',4,4',5,5'-HpCB 189 0.2 1.0 5.0 50 400 2000
2,21,3,3',5,5',6,6'-OcCB 202 0.2 1.0 5.0 50 400 2000
2,3,3',4,4',5,5',6-OcCB 205 0.2 LO 5.0 50 400 2000
2,2',3,3',4,4',5,5',6-NoCB 206 0.2 1.0 5.0 50 400 2000
2,2',3,3',4',5,5',6,6'-NoCB 208 0.2 LO 5.0 50 400 2000
DeCB 209 0.2 L.0 5.0 50 400 2000
Labeled ToxicifLOC/window-defining
13C,2-2-MoCB 1L 100 100 100 100 100 100
"C12-4-MoCB 31, 100 100 100 100 100 l00
"C12 2,2'-DiCB 41, 100 100 100 100 100 100
"C12-4,4'-DiCB 15L 100 100 100 100 100 l00
"C12-2,2',6'-TrCB 19L 100 100 100 100 100 100
13C12-3,4,4'-TrCB 37L 100 100 100 100 100 100
11C,z 2,2',6,6'-TeCB 54L 100 100 100 100 100 100
13C12-3,31,4,4'-TeCB 77L 100 100 100 100 100 100
'3C12-3,4,4',5-TeCB 81L 100 100 100 100 100 100
`Q, 2,2',4,6,6'-PeCB 104L 100 100 100 100 100 100
11C12-2,3,3',4,4'-PeCB 105L 100 100 100 100 100 100
13C,,-2,3,4,4',5-PeCB 114L 100 100 100 l00 100 100
"C,Z 2,3',4,4',5-PeCB 118E 100 100 100 l00 100 100
"C,2-2',3,4,4',5-PeCB 123L 100 100 100 l00 l00 100
"C,2-3,3',4,4',5-PeCB 126E 104 106 100 lp0 l00 100
91
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
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Solution concentration (ng lmL)

CB congener
IUPAC' CS-0.2
(Hi sens)z
CS-1
CS-2 CS-3
(VER)
CS-4
CS-5
"C12-2,2',4,4',6,6'-HxCB 155L 100 100 100 100 100 100
13C12-2,3,3',4,4%5-HxCB 156L 100 100 100 100 100 100
"C12 2,3,31,4,4',5'-HxCB 157L 100 100 100 100 100 100
"C12-2,3',4,4',5,5'-HxCB 167L 100 100 100 100 100 100
" C,Z 3,3',4,4',5,5'-HxCB 169L 100 100 100 100 100 100
13C,2-2,21,3,4',5,6,6'-HpCB 188L 100 100 100 100 100 100
13C12-2,3,3',4,4',5,5'-HpCB 189L 100 100 100 100 100 100
"C12-2,2',3,3',5,5',6,6'-OcCB 202L 100 100 100 100 100 100
"C,Z 2,3,3',4,4',5,5',6-OCCB 205L 100 100 100 100 100 100
"C,2-2,2',3,3',4,4',5,5',6-NoCB 206L 100 100 100 100 100 100
13C,2-2,2',3,3',4',5,5',6,6'-NoCB 208L 100 100 100 100 100 100
"C,2-DeCB 209L 100 100 100 100 100 100
Labeled clean-up
13C,2-2,4,4'-TrCB 28L 100 100 100 100 100 100
"C,= 2,3,3',5,5'-PeCB 1111- 100 100 100 100 100 100
"C12-2,2',3,3',5,5',6-HpCB 178L 100 100 100 100 100 100
Labeled injection internal
15C12 2,5-DiCB 9L 100 100 100 100 100 100
13C13 2,2',5,5'-TeCB 52L 100 100 100 100 100 100
"C12-2,2',4',5,5'-PeCB 1011, 100 100 100 100 100 100
13C1z 2,2',3',4,4',5'-HxCB 138L 100 100 l00 100 100 i00
13C12 2,2',3,3',4,4',5,5'-OcCB 194L 100 100 100 100 100 l00
Suffix "L" indicates labeled compound
Additional concentration used for calibration of high sensitivity HRGCIHRMS systems
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 56 of 63
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Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 57 of 63
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Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 58 of 63
Table 7. Scan descriptors, levels of chlorination, m/z information, and substances monitored by
HRGCIHRMS
Function and
chlorine level
mlz
mlz type
mlz formula
Substance
Fn-1; Cl-1 188.0393 M 12C12 H9 35C1 Cl-1 CB
190.0363 M+2 12C 12 H, 3701 Cl-1 CB
200.0795 M "Ci2 H, 35C1 i3C12 Cl-1 CB
202.0766 M+2 13C12 H9 37c1 '3012 Cl-1 CB
218.9856 lock C, F9 PFK
Fn-2; C1-2,3 222.0003 M 12C12 Hg 35012 0-2 PCB
223.9974 M+2 '2012 Hs 350137 Cl C1-2 PCB
225.9944 M+4 12C12 H8 37C12 CI-2 PCB
234.0406 M 13012 H, 35012 "C12 CI-2 PCB
236.0376 M+2 13C12 H, 35C1 37 Cl "C,2 CI-2 PCB
242.9856 lock C6 F9 PFK
255.9613 M 12C12 H7 35C13 CI-3 PCB
257.9584 M+2 12012 H, JSCIz 3701 Cl-3 PCB
Fn-3 255.9613 M 17C12 H, 35013 CI-3 PCB
CI-3,4,5 257.9584 M+2 12C12 HT 35012 37G Cl-3 PCB
259.9554 M+4 12C12 H7 35C137C12 G-3 PCB
268.0016 M 13C12 H7 35C13 "C12 CI-3 PCB
269.9986 M+2 13C12 H7 3512 37C1 13C12 CI-3 PCB
280.9825 lock C6 1711 PFK
289.9224 M 1X12 H6 35C1 CI-4 PCB
291.9194 M+2 12C12 H6 35C13 3701 Cl-4 PCB
293.9165 M+4 12C12 H6 35C12 37012 G-4 PCB
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 59 of 63
Function and
chlorine level
mlz
mlz type
mlz formula
Substance
301.9626 M 13012 H' -Cl4 130,2 C1-4 PCB
303.9597 M+2 13012 H6 35C13 "Cl 13C12 CI-4 PCB
323.8834 M 12C12 H5 35C15 C1-5 PCB
325.8804 M+2 12C 12 H5 "Cl, "CI C1-5 PCB
327.8775 M+4 "C, H5 35C13 3X12 Cl-5 PCB
337.9207 M+2 13012 H5 35C14 37CI 13012 Cl-5 PCB
339.9178 M+4 13012 H5 35C13 37CI, 13C12 0-5 PCB
Fn-4 289.9224 M 12012 H6 35C+14 CI-4 PCB
C14,5,6 291.9194 M+2 12C12 H6 35C13 3701 Cl-4 PCB
293.9165 M+4 12012 H6 35C12 37C12 CI-4 PCB
301.9626 M+2 13CI2 H6 35C13 3701 13`-+12 C1-4 PCB
303.9597 M+4 13C12 H6 35C12 37.12 13012 CI-4 PCB
323.8834 M 12C12 H5 35C15 0-5 PCB
325.8804 M+2 12C12 H5 35C14 37CI C1-5 PCB
327.8775 M+4 12012 H5 35C13 37012 CI-5 PCB
330.9792 lock C7 F15 PFK
337.9207 M+2 13C12 H5 35C14 37CI 13C12 CI-5 PCB
339.9178 M+4 13C12 HS -"Cl, 37C12 13012 CI-5 PCB
359.8415 M+2 13CI2 H4 35C15 37CI 0-6 PCB
361.8385 M+4 13C12 H4 35C14 37012 CI-6 PCB
363.8356 M+6 13C12 H4 35C13 37CL C1-6 PCB
371.8817 M+2 13C12 H4 35cl5 37CI 13C12 C1-6 PCB
373.8788 M+4 13C 12 H4 35C14 37CI, 13C12 C1-6 PCB
Fn-5 323.8834 M 12C12 H5 35C15 CI-5 PCB
96
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 60 of 63
Function and
chlorine level
mlz
mlz type
mlz formula
Substance
C1-5,6,7 325.8804 M+2 1X12 HS 35C14 37CI CI-5 PCB
327.8775 M+4 12C12 HS 31CI3 37CI, CI-5 PCB
337.9207 M+2 13012 H5 35CI4 37CI 13012 0-5 PCB
339.9178 M+4 nC12 H5 35C13 37011 13C12 CI-5 PCB
354.9792 lock C9F13 PFK
359.8415 M+2 12012 H4 35CI5 3701 CI-6 PCB
361.8385 M+4 12C12 H4 35C14 37C12 CI-6 PCB
363.8356 M+6 12c12 H4 35C13 37 C13 CI-6 PCB
371.8817 M+2 13012 H4 35C15 37a 13C12 Cl-6 PCB
3718788 M+4 13012 H4 35cL 37CI, 13012 CI-6 PCB
393.8025 M+2 12012 1-13 35CI6 3701 C1-7 PCB
395.7995 M+4 12012 H3 35C15 37C12 CI-7 PCB
397.7966 M+6 12C12 H3 35CI4 37C13 CI-7 PCB
405.8428 M+2 13C12 H3 33q 37CI 13C12 C1-7 PCB
407.8398 M+4 13C12 H3 35{.15 37012 130,2 C1-7 PCB
454.9728 QC C11 Fl7 PFK
Fn-6 393.8025 M+2 12C12 H3 35CI6 3701 CI-7 PCB
C1-7,8,9,10 395.7995 M+4 12C12 H3 35C15 37011 Cl-7 PCB
397.7966 M+6 1X12 H3 35c14 37013 CI-7 PCB
405.8428 M+2 13012 H3 35CI6 37CI 13C12 C1-7 PCB
407.8398 M+4 13C12 H3 35015 37c12 13012 0-7 PCB
427.7635 M+2 12CI2 H2 35CI7 37CI 0-8 PCB
429.7606 M+4 12012 H2 35016 37C12 CI-8 PCB
431.7576 M+6 12C12 H2 35c15 37CI3 CI-8 PCB
97
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 61 of 63
Function and
chlorine level
m/z
m/z type
m/z formula
Substance
439.8038 M+2 13 C,2 H2 35C1, 3701 1}C12 C1-8 PCB
441.8008 M+4 13C32 H2 MCI, 37CI, 13C12 C1-8 PCB
442.9728 QC C,o F,3 PFK
454.9728 lock C„ F,3 PFK
461.7246 M+2 12012 H, 35C18 37C1 CI-9 PCB
463.7216 M+4 12C12 HI 3501, 37C1, CI-9 PCB
465.7187 M+6 12012 H, 75016 37013 CI-9 PCB
473.7648 M+2 13C12 H, 35CI8 3701 13012 Cl-9 PCB
475.7619 M+4 13012 Hl 3517 37C12 13012 Cl-9 PCB
495.6856 M+2 13012 H4 35C4 37C1 C1-10 PCB
497.6826 M+4 12012 3501$ 37012 C1-10 PCB
499.6797 M+6 12012 35017 77C13 C1-10 PCB
507.7258 M+2 13C12 H4 35CI8 3701 13012 Cl-IO PCB
509.7229 M+4 13012 H4 35CI8 37c12 13012 CI-10 PCB
511.7199 M+6 1512 H4 35018 37014 13012 CI-10 PCB
1. Isotopic masses used for accurate mass calculation
1H
12C
13c
3501
37cl
19F
1.0078
12.0000
13.0034
34.9689
36.9659
18.9984
98
Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 62 of 63
7'aN0 S. II1??=ka3 Lom aFund aiir-c rm IILtq and . IJA:'t?
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Determination of PCBs Congeners by 1668A
Pace Analytical Services, Inc. Date: Upon Final Signature
S-MN-H-014-Rev.08 Page: 63 of 63
Table 9. Suggested Sample Quantities to be Extracted for Various Matrices'

Sample matriX2
?Xample Percent
solids
Phase Quantity
extracted
Single-phase
Aqueous rinkin water
73roundwater <1 -3 1000 ml:
reated wastewater
olid soil
om st X20 Solid log
sh
Organic Waste solvent
Waste oil <1 Organic 10 g
r anic polymer
issue ish
i
O
10

uman adipose - rgan
c g
ulti- hase
i uid/Solid
queous/Solid et soil
ntreated effluent
i ested municipal sludge 1-30 Solid 10 g
iiter cake
-per pulp
Organic/solid ndustrial sludge 1
100 B
th 10

it waste - o g
I uidlLi uid
queous/organic n- process effluent
ntreated effluent <1 Organic 10 g
rum waste
queouslorganiclsolid ntreated effluent >1 O
i
&
lid 10

rum waste rgan
c
so g
1. The quantity of sample to be extracted is adjusted to provide 10 g of solids (dry weight). One liter of aqueous
samples containing one percent solids will contain 10 grams of solids. For aqueous samples containing
greater than one percent solids, a lesser volume is used so that 10 grams of solids (dry weight) will be
extracted.
2. The sample matrix may be amorphous for some samples. In general, when the CBs are in contact with at
multi-phase system in which one of the phases is water, they will be preferentially dispersed in or adsorbed on
the alternate phase because of their low solubility in water.
3. Aqueous samples are filtered after spiking with the labeled compounds. The filtrate and the materials trapped
on the filter are extracted separately, and the extracts are combined for cleanup and analysis.
aceAnalytical'N
I www.pacelabs.com
i
STANDARD OPERATING PROCEDURE
Pace Analytical Services, Inc.
1241 Bellevue Street
Green Bay, WI 54302
Phone: [phone]
Fax: [phone]
Analysis of Polychlorinated Biphenyls (PCBs) by Gas Chromatography
Reference Methods: SW-846 Method 8082
SOP NUMBER:
EFFECTIVE DATE:
SUPERSEDES:
S-GB-0-026-Rev. I
Date of Final Signature
GB-0-026-Rev.0
APPROVAL
/ G
A 0 7
Nils Melberg, General Manager Date

Arthur F. Lautenbach, Quality Manager
SNI,6-7
Date
© 2002-2007, Pace Analytical Services, Inc. This Standard Operating Procedure may not be reproduced, in part or in full,
without written consent of Pace Analytical Services, Inc. Whether distributed internally or as a "courtesy copy" to clients or
regulatory agencies, this document is considered confidential and proprietary information.
Any printed documents in use within a Pace Analytical Services, Inc. laboratory have been reviewed and approved by the persons
listed on the cover page. They can only be deemed official if proper signatures are present.
This is COPY# 16 distributed on J 1//Z /17 by 4 4`" and is CONTROLLED or X UNCONTROLLED.
S-GB-0-026-Rev. I
Table of Contents
1. Purpose ....................................................................................................................................3
2. Scope and Application ...........................................................................................................3
3. Summary of Method ..............................................................................................................3
4. Interferences ...........................................................................................................................3
5. Safety .......................................................................................................................................4
6. Definitions ...............................................................................................................................4,
7. Responsibilities and Distribution ..........................................................................................5
8. Sample Collection, Preservation and Handling ..................................................................5
9. Reagents and Standards ........................................................................................................5
10. Equipment and Supplies ...................................................................................................6
11. Calibration ..........................................................................................................................7
12. Procedure ............................................................................................................................9
13. Quality Control ...............................................................................................:................12
14. Method Performance .......................................................................................................14
15. Pollution Prevention and Waste Management ..............................................................14
16. References .........................................................................................................................14
17. Tables, Diagrams, Flowcharts, Appendices, Addenda etc ...........................................15
18. Revisions ...........................................................................................................................17
Pace Analytical Services, Inc. - Green Bay Laboratory
Analysis of PCBs by GC
S-GB-0-026-Rev. l
File: S-GB-0-026Revl.doc
Date: May 3, 2007
Page 3 of 18
1. Purpose
1.1 The purpose of this Standard Operating Procedure (SOP) is to determine the
concentration of PCBs in water, soil, sediment, waste, and biological samples in
accordance with SW846 Method 8082. Samples for analysis are prepared by SW846
Method 3510C, 3540C, 3541, 3545, 3550B and 3580A.
2. Scope and Application
2.1 This method is used to determine the concentration of PCBs in extracts prepared
from water, soil, sediment, waste, and biological samples. A list of the Aroclors
routinely analyzed, their CAS numbers and Pace Reporting Levels (PRLs) are shown
in Section 17, Table A. PRLs are subject to change based on current analytical
system performance and actual sample matrices.
2.2 This procedure is restricted to use by, or under the supervision of, analysts
experienced in the use of gas chromatograph/electron capture detection (GC/ECD)
systems and interpretation of complex chromatograms. Each analyst must
demonstrate the capability to generate acceptable results with this method to be
considered qualified to report sample results
3. Summary of Method
3.1 Sample extracts are prepared for analysis by the appropriate sample preparation
method. The procedures for extract preparation are described in separate SOPs. A
volume of sample extract is injected into a GC and compounds in the effluent are
detected by an ECD based on an operating program set up to achieve optimum
separation and quantitation of target analytes.
3.2 Retention time windows, in combination with characteristic elution patterns from a
dual-column analysis, are used in the identification of PCBs as Aroclors.
3.3 PCBs are quantified as Aroclor mixtures by comparison of their ECD response on a
single column with a calibration curve(s) constructed from the response(s) of
authentic standards.
3.4 Results are reported in parts per billion (µg/kg or µg/L). Soil and sediment sample
results are corrected for moisture and reported on a dry weight basis. Biological
results are reported based on wet weight, or "as is" basis.
4. Interferences
4.1 Method interferences may be caused by contaminants (primarily phthalate esters) in
solvents, reagents, glassware and other sample processing hardware that leads to
discrete artifacts and/or elevated baselines. Phthalate esters are common
contaminants that result from contact with flexible plastics. Contact with common
plastics or rubber products must be avoided. Lab ware should be constructed of
glass, stainless steel, or PTFE, must be thoroughly cleaned and dried prior to use, and
should be rinsed with the appropriate solvent immediately before use.
Pace Analytical Services, Inc. - Green Bay Laboratory
Analysis of PCBs by GC
S-GB-0-026-Rev. l
File: S-GB-0-026Revl.doc
Date: May 3, 2007
Page 4 of 18
4.2 Elemental sulfur is a common environmental contaminant in many soil, sediment and
leachate samples, producing a broad peak that will confound analysis of early eluting
analytes. Sulfur may be removed from extracts by treatment with elemental mercury,
copper powder, or similar procedure described in a separate SOP.
4.3 Waxes, lipids, and other similar high molecular weight materials may be co?extracted
from samples typically resulting in baseline elevation during GC analysis. These
interferences may be removed by sulfuric acid clean up and/or column
chromatography cleanup using Florisil or gel permeation chromatography (GPC), all
of which are described in separate SOPs. Other halogenated pesticides and similar
industrial chemicals, which can interfere with analytes of interest, may be removed
by these procedures as well.
4.4 All solvents, reagents, glassware, and sample processing hardware must be routinely
demonstrated to be free from interferences under the conditions of the analysis by
monitoring method blanks and taking corrective action as required.
5.
Safety
5.1 The toxicity, or carcinogenicity, of many chemicals used in this method has not been
precisely defined; each chemical should be treated as a potential health hazard, and
exposure to these chemicals should be minimized. Each analyst is responsible for
maintaining awareness of OSHA regulations regarding safe handling of chemicals
used in this method. Reduce exposure by the use of gloves, lab coats and safety
glasses. Material Safety Data Sheets (MSDSs) are on file in the laboratory and
available to all personnel.
5.2 Take precautions when handling samples. Samples should always be treated as
potentially hazardous. The use of personal protective equipment (gloves, lab coats
and safety glasses) is required when handling samples.
5.3 A reference file of Material Safety Data Sheets (MSDS) is made available to all
personnel involved in the chemical analysis, and is located at the front desk. A formal
safety plan has been prepared and is distributed to all personnel with documented
training.
5.4 PCBs have been tentatively classified as known or suspected human or mammalian
carcinogens. Primary standards of these toxic compounds should be prepared in a
hood.
6.
Definitions
6.1 All applicable definitions can be found in Section 10.0 of the PASI Quality Manual.
6.2 Extract - A solution of contaminants extracted and concentrated from a sample.
Pace Analytical Services, Inc. - Green Bay Laboratory File: S-GB-0-026Revl.doc
Analysis of PCBs by GC Date: May 3, 2007
S-GB-0-026-Rev.1 Page 5 of 18
7. Responsibilities and Distribution
7.1 Analyst - Any analyst using this procedure is responsible for reading, understanding
and following this SOP. Any deviation from this SOP must be reported to the
appropriate Supervisor. The analyst must make their recommendations for changing
the SOP to their supervisor or the QM in writing.
7.2 General Manager - The General Manager must ensure that all analysts are properly
trained and qualified to use this procedure. The General Manager is also responsible
to ensure that the SOP is followed. The General Manager is responsible for
reviewing the SOP and communicating recommended changes to the QM.
7.3 Quality Manager (QM) - The QM is responsible for monitoring the implementation
of the SOPs and the associated good laboratory practice. The QM will participate in
the revision of the SOP and make sure it is current. The QM will review and approve
all SOPS.
7.4 Distribution - The official version of this SOP is the signed hardcopy version found
in the laboratory. A copy of the SOP shall be kept in the appropriate department for
reference.
7.5 Revision - This SOP will be reviewed every two years at a minimum. It will also be
revised as needed if procedures or methods change.
8. Sample Collection, Preservation and Handling
8.1 General Procedures - Procedures for sample collection, preservation, and handling
are described in the separate sample preparation SOPS.
8.2 Holding Times
8.2.1 Water Samples - Samples must be extracted within 7 days of collection.
8.2.2 Soil, Solid, and Other Waste Samples - Samples must be extracted within
14 days of collection.
8.2.3 Biological Samples - Samples remain frozen for up to one year or longer per
client request prior to extraction; typical extraction hold times do not apply.
8.2.4 Extracts - Extracts must be analyzed within 40 days of preparation.
8.3 Sample Storage - Store all samples and extracts in the dark at 4 ± 2°C. Biological
samples must be stored at or below 0°C until extracted.
9. Reagents and Standards
9.1 Solvents - Hexane and acetone, pesticide grade (Section 17, Table B). All solvents
are stored at room temperature and environmental conditions.
Pace Analytical Services, Inc. - Green Bay Laboratory
Analysis of PCBs by GC
S-GB-0-026-Rev.1
File: S-GB-0-026Revl.doc
Date: May 3, 2007
Page 6 of 18
9.2 Analytical Standards - Prepared from stock standard solutions and are required for
initial calibration and continuing calibration checks (Section 17, Table Q. The
following describes the contents of each type of solution:
9.2.1 Calibration and Calibration Check Standards- Five concentration levels
of calibration solutions are prepared containing equal amounts of Aroclors 1016
and 1260 (combined in the same solution named AR1660 throughout this
document), as well as the surrogates decachlorobiphenyl (DCB) and 2,4,5,6-
tetrachloro-m-xylene (TMX). A single point calibration standard is required for
the other Aroclor mixtures preferably at the mid-point level of the AR1016/1260
curve. A calibration check solution (ICV) is also prepared at the mid-level
concentration of AR1016/1260 from second source materials.
9.2.2 Surrogate Standard Spiking Solution - contains decachlorobiphenyl
(DCB) and 2,4,5,6-tetrachloro-m-xylene (TMX) and is spiked into all samples
prior to extraction.
9.2.3 Matrix Spiking Solutions - contain an Aroclor mixture that is spiked into
all appropriate QC samples (LCS, MS, and MSD) prior to extraction. The
Aroclor(s) spiked and/or spike amounts may be adjusted when prior knowledge
of the type or concentration of Aroclor(s) present in the sample matrix is known,
or to comply with project requirements.
9.3 Preparation of Analytical Standard Solutions - Standards are prepared from
commercially available stock solutions. The sources of the stock solutions, recipes
for preparing dilutions and working standards, and concentrations in all solutions are
shown in Section 17, Table D. All standards are prepared in hexane and stored in
amber vials with PTFE-lined screw caps at 4 °C or colder.
9.4 Stability of Analytical Standards - Stock solutions of Aroclor mixtures must be
replaced within 1 year of preparation. All dilutions and working standard solutions
must be replaced within 6 months of preparation or sooner if the standards show
signs of degradation. As each standard from the vendor is opened, record all
pertinent information in the stock standard logbook. Record all standard preparations
in the working standard logbook
10. Equipment and Supplies
10.1 Instrumentation
10.1.1 GC -Hewlett Packard (HP) 5890 equipped with dual ECDs or HP 6890
equipped with dual gECDs.
10.1.2 GC Autosampler - HP 7673A (5890) or HP 7863 (6890).
10. 1.3 GC Columns - Two of the following capillary columns may be used:
10.3.1.1 RTX CLPesticides I, 30m x 0.32mm I.D. (Restek)
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10.3.1.2 RTX CLPesticides II, 30m x 0.32mm I.D. (Restek)
10.3.1.3 D13- 1701, 30m x 0.32mm I.D. (J&W Scientific)
10.3.1.4 DB-5, 30m x 0.32mm I.D. (J&W Scientific)
10. 1.4 Data Processor - TurboChrom IV or HP ChemStation.
10.1.5 Printer - HP LaserJet 5Si or equivalent.
10.2 Glassware and Materials
10.2.1 Gastight Syringes - any size ranging from 10µL to 1000µL (Hamilton
series 1000 or equivalent)
10.2.2 Autosampler Vials - 1.8mL with crimp caps
11. Calibration
11.1 Initial Calibration (ICAL)
11. Analysis of Standards
11.1.1.1 The initial calibration includes analysis of a five-point
calibration curve of AR 1660 at concentrations of 0. 1, 0. 3, 0.5, 0.8, and
1.0µg/ml,, which includes TMX and DCB at concentrations of 0.01, 0.02,
0.05, 0. 1, and 0.15µg/mL respectively. Inject a single point standard of
Aroclors 1221, 1232, 1242, 1248, 1254, 1262 and 1268 at 0.5µg/mL.
11.1.1.2 Other calibration ranges may be substituted to meet expected
concentrations of samples to be analyzed. If historical data indicates a
specific Aroclor is present, a five point initial calibration may be performed
for the Aroclor of concern instead of using the AR 1660 mixture.
11.1.1.3 A minimum of five (preferably seven) peaks must be selected for
each Aroclor. The peaks chosen for quantitation should be at least 25% of
the height of the largest peak in each Aroclor and should have minimal co-
elution with the peaks of other Aroclors.
11. 1.2 Retention Time (RT) - Retention time windows are used for compound
identifications in samples. The RT for all components in all standards must be
within the windows specified for both columns.
11.2.1.1 Make at least three injections of all analytes of interest over a 72-
hour period.
11.2.1.2 Record the retention time for each selected peak for each Aroclor
mixture, to three decimal places. Calculate the mean and standard deviation
for each peak.
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11.2.1.3 The width of the retention time window is defined as± 3
standard deviations of the mean established. The minimum retention
window will be + 0.03 minutes.
11.2.1.4 Establish the center of the RT window for each Aroclor mixture
and surrogate using the absolute RT from the calibration verification
standard at the beginning of the analytical shift. Optionally, the Initial
Calibration RT windows may continue to be used as long as method criteria
are met. For samples run during the same shift as an initial calibration, use
the RT of the mid-point standard in the Initial calibration as the center of the
RT window.
11. 1.3 Response Factors (RF) - Individually tabulate the area responses for each
of the five or more peaks selected for each Aroclor versus concentration of the
five-point calibration standards for each GC column. Calculate RF for each peak
using the following equation:
fix
Cx
Where:
A,,= Total area of analyte response.
C,? = Concentration of the analyte in the solution (µg/mQ.
11. 1.4 Acceptance Criteria - The percent relative standard deviation (%RSD) of
the five calibration factors for each peak of each Aroclor, (1016 and 1260) along
with the surrogates must be < 20%. If this is the case, linearity can be assumed,
and the average RF can be used for quantitation. If the %RSD is >20%, a linear
calibration curve may be used if the correlation coefficient is > 0.99. The results
for both columns must meet calibration acceptance criteria.
11.2 Calibration Verification
11.2.1 Initial Calibration Verification (ICV)- In order to consider the initial
calibration acceptable, an ICV standard must be analyzed. The ICV standard must
be from a second source stock and meet the same criteria as the continuing
calibration verification standard before the initial calibration may be considered
valid.
11.2.2 Continuing Calibration Verification (CCV) -A midpoint calibration
check standard must be injected at the beginning and end of each 12-hour
analysis period, and at intervals of not less than once every 20 samples, for
calibration verification. If the response factor (area/concentration) of the check
standard deviates by more than 15% from the initial average response factor, the
calibration is considered out of control and analysis must be stopped.
11.2.3 Acceptance Criteria - The percent difference (%D) is determined for every
analyte and must be within ±15% of the calibration curve. Calculate %D for
each peak using the following equation:
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R2)X100
%D = (Ri R-i J
Where:
R, = Mean Response factor from the ICAL
R2 = RF calculated from the CCV
11.2.3.1. First determine whether the average %D for all of the peaks for each
specific Aroclor with a five-point calibration is < 15%. Each individual
Aroclor must be evaluated separately. For example, the average %D for
all of the peaks used for quantitation of AR1016 must be _< 15%. If the
Aroclors themselves are acceptable, evaluate the %RSD for each
surrogate. If the %D is < 15% for each individual Aroclor and surrogate,
the continuing meets the acceptance criteria.
11.2.3.2. If the ending calibration verification standard exceeds 15%D criteria on
the high side (i.e., an increase in sensitivity) samples that had no
Aroclors detected do not need to be reanalyzed. If the continuing
calibration standard criterion is exceeded on the low side (i.e., a drop in
sensitivity), all samples analyzed since the last acceptable CCV must be
re-analyzed.
11.2.4 All samples must be bracketed by acceptable calibration verifications on
both columns. Perform corrective action such as injection port or column
maintenance. Prior to the analysis of any subsequent samples acceptable
calibration verification must be established. In the event that this cannot be
achieved, a new initial calibration must be performed.
12
Procedure
12.2 Sample Preparation - All sample extracts and standard solutions must be allowed
to warm to room temperature before analysis.
12.3 GC/ECD System Preparation - Verify instrument parameters as set up for current
operating conditions.
12.3.1 GC Column Conditions
Carrier Gas UHP Helium
Flow Rate 3.4 mL/min.
Make-up Gas UHP Nitrogen
Flow Rate 35.0 mL/min.
Detector Temp. 300°C
Injector Temp. 205°C
Injection Splitless
12.3.2 GC Temperature Program
Initial Temp. 110°C
Initial Time 1.5 min.
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Rate 1 20.00°C/min.
Final Temp.1 140°C
Final Time 1 0.00 min.
Rate 2 11.00°C/min.
Final Temp. 2 280°C
Final Time 2 5.00 min.
Rate 3 20.00°C/min.
Final Temp. 3 300°C
Final Time 3 3.00 min.
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12.4 Batch Sequence - Generate a sequence to run a batch of samples and the associated
quality control samples.
12.4.1 Initial Calibration - For example, the batch for initial calibration should
include the following:
Series of 2-3 Primes
Solvent Blank (Hexane)
AR1660-1 (0.1µg/mL)
AR1660-2 (0.3gg/mL)
AR1660-3 (0.5µg/mL)
AR1660-4 (0.8µg/mL)
AR1660-5 (1.0µg/mL)
Solvent Blank (Hexane)
AR1660-3 ICV
12.4.2 Sample Analysis - For example, the typical batch for analysis of PCBs should
include the following:
AR1660-301 CCV (0.51tg/mL)
(20 samples or 12-hour period)
Method Blank
Laboratory Control Spike
Samples
Matrix Spike/Matrix Spike Duplicate
Duplicate Sample(s)
AR1660-302 CCV (0.5µg/mL)
12.5 Load Autosampler - Load the autosampler with the appropriate primes, solvent
blanks, standards and samples for the batch as it was created.
12.6 Analyze Samples - Analyze all standards, quality control samples, and
environmental samples.
12.6.1 The method blank and LCS extracted along with the samples should be
analyzed on the same instrument as the samples.
12.6.2 If the analyst determines that interferences could be removed by sulfuric acid
cleanup and/or sulfur removal, then the analyst will perform the necessary
cleanups and re-analyze the samples. The blank and LCS will also undergo the
same cleanups and be re-analyzed.
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12.7 Qualitative Analysis of Results
12.7.1 Identification
12.6.1.1 To be identified as an Aroclor, peaks present in a sample extract must
fall within the established retention time window for a specific Aroclor. Once
the Aroclor pattern has been tentatively identified, compare the responses of 3 to
10 major peaks in the single-point calibration standard for that Aroclor with the
peaks observed in the sample extract. Overlay comparison of sample
chromatograms with standard chromatograms may be required to clearly identify
patterns.
12.6.1.2 Since the chromatograms for many Aroclor mixtures overlap, the
presence of multiple mixtures may complicate their quantitation. Also,
environmental "weathering" of PCBs may complicate reliable identification and
quantitation.
12.7.2 Confirmation
12.6.2.1 Confirmation is generally required using a second GC column of
dissimilar stationary phase. When dual-column analysis is performed for
confirmation, the same initial and continuing calibration criteria apply to
both columns. If analyte concentrations are sufficient, identifications may be
confirmed by GC/MS by analyzing the same extract by SW846 Method 8270.
12.6.2.2 Since Aroclors provide distinct multiple peak patterns which may be
identified by an experienced analyst, confirmation on the second column may be
based upon pattern recognition.
12.8 Calculate Results
12.8.1 The amount of Aroclor is calculated using the individual response factor
(single point) for each of the 7 characteristic peaks chosen for quantitation of
that specific Aroclor. If Aroclor 1016 and/or 1260 is being quantified use the
average response factor from the AR 1660 curve. Use the single point response
factor from the initial calibration for all other Aroclors. Surrogates are
quantified based on the average response factors for TMX and DCB analyzed
with the AR1660 curve. A concentration is determined using each of the
characteristic peaks and then those 7 concentrations are averaged to determine
the on-column concentration of that Aroclor.
12.8.2 If the initial on-column result of a sample extract exceeds the calibration
range, the extract must be diluted and re analyzed. All dilutions should keep
the response of the major constituents in the upper half of the linear range of
the curve. The GC data system will calculate concentration of each parameter
as µg/nil, on-column in the extract. Concentrations in samples are then
calculated based on sample size, total volume of the final extract, any dilution
factor, and any correction factor.
12.8.2.1 Water and Water-Miscible Waste Samples
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Final Concentration (uglL) (C. XDFXUfXV )
(Vixv )
Where:
Cx = On-column concentration in extract (µg/ml,).
DF = Dilution factor.
Uf = Correction factor.
Vt = Volume of final extract (µL).
Vi = Volume injected (µL).
V. = Volume of water sample extracted (mL).
12.8.2.2Soil/Solid, Waste and Biological Samples
Final Concentration /g _ (CxXDFXUfXV)
(,ug g) (VXWSXS)
Where:
C, = On-column concentration in extract (µg/mL).
DF = Dilution factor.
Uf= Correction factor.
Vt = Volume of final extract (µL).
Vi = Volume injected (µL).
W, = Weight of sample extracted (g).
S = Percent Solids (biological samples not corrected for percent solids).
12.9 Quality Control Results - Calculate recoveries for the surrogates in all samples;
spiked analytes in LCS and MS/MSD samples; and Relative Percent Differences
(RPD) for duplicate and MS/MSD samples.
13 Quality Control
13.3 Calibration Checks
13.3.1 ICAL - If initial calibration criteria are not met, check standards preparation
procedure for errors. Prepare new standards as required and re-run the
calibration.
13.3.2 Continuing Calibration Verification - If the CCV criteria are not met, check
system parameters, identify and correct likely causes, and rerun the check.
An acceptable check is required to report sample results for the applicable
batch.
13.4 Surrogate Recoveries - Surrogate compound(s) must be added to all samples, spikes,
control samples and method blanks, prior to analysis as indicators of method accuracy.
Laboratory-based accuracy limits should be used for acceptance criteria. If these criteria
are not met, check system parameters, identify and correct likely causes, and re-run
the samples.
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13.4.1 If both surrogate recoveries fail this criterion, re-extraction of the sample may
be necessary. If surrogate recoveries are higher than the acceptance criteria
and target compounds are less than the reporting limit, the results may be
reported with an appropriate footnote. If recoveries appear out of control due
to sample matrix, report the results with an appropriate footnote.
13.4.2 One surrogate is allowed to be outside of the control limits. For instance, if an
interfering peak obscures one surrogate, then that one surrogate may be
excluded. The surrogate is considered diluted out and not evaluated when the
dilution performed brings the theoretical on-column concentration below the
concentration of the low standard in the initial calibration curve.
13.5 Method Blank -The method blank must not contain analyte responses at or above the
reporting limit. If the results are not acceptable, re-analyze the method blank. If the
problem persists, conduct maintenance to clean the analytical system. An acceptable
method blank is required to report sample results for the applicable batch.
13.5.1 The method blank must meet the surrogate limits. If the blank fails this
criterion, all of the associated samples, matrix spikes and laboratory control
spikes will be evaluated and a corrective action will be determined.
13.5.2 If the blank contains any analyte of interest above the reporting limit, all of the
associated samples, matrix spikes, and laboratory control spikes must be re-
extracted unless the sample concentration is greater than 20X the amount
found in the blank or the analyte is not detected in an associated sample. For
Wisconsin projects this criteria will be "Above the LOD".
13.6 LCS Recoveries - One LCS must be analyzed with each batch of 20 samples.
Laboratory-based accuracy limits should be used to for acceptance criteria. An
acceptable LCS is required to report sample results for the applicable batch.
13.6.1 If the laboratory control spike does not meet the recovery criteria, the results
of all QC performed with the batch will be evaluated by the analyst.
Corrective actions include re-extraction of the samples or reanalysis of the
extracts.
13.7 One LCSD must be analyzed with each batch of 20 samples if inadequate sample is
available to perform a MS/MSD. Laboratory-based accuracy limits should be used to
for acceptance criteria. An acceptable LCSD is required to report sample results for
the applicable batch.
13.8 MS/MSD Recoveries - One MS/MSD pair should be analyzed with each batch of 20
samples. Laboratory-based accuracy limits should be used to for acceptance criteria.
The sample use for the MS/MSD pair is either determined by the client or selected at
random from client samples as sample volume allows.
13.8.1 If a matrix spike recovery fails this criterion, the recovery of the other spiked
sample in the MS/MSD pair should be evaluated. If recovery failures are
duplicated then the sample matrix is suspected as the problem and the data
should be flagged and the failures discussed in the sample narrative.
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13.9 Duplicate and MS/MSD RPDs - Five percent of all environmental samples should
be analyzed in duplicate. A MS/MSD pair is also an acceptable duplicate analysis. If
results are not acceptable, check for possible sample preparation problems and re-
analyze if needed. Report the results with an appropriate data qualifier.
14 Method Performance
14.3 There are several requirements that must be met to insure that this procedure
generates accurate and reliable data. A general outline of requirements has been
summarized below. Further specifications may be found in the Laboratory Quality
Manual.
14.3.1 The analyst must read and understand this procedure with written
documentation maintained in his/her training file.
14.3.2 An initial demonstration of capability (IDC) must be performed per ALL-Q-
020, Training Procedures. A record of the IDC will be maintained in his/her
QA file with written authorization from the Laboratory Manager and Quality
Manager.
14.3.3 An annual method detection limit (MDL) study will be completed per ALL-Q-
004, Method Detection Limit Studies, for this method and whenever there is a
major change in personnel or equipment. The results of these studies are
retained in the quality assurance office.
14.3.4 Periodic performance evaluation (PE) samples are analyzed per ALL-Q-010,
Proficiency Testing Program, to demonstrate continuing competence. All
results are stored in the QA office.
15 Pollution Prevention and Waste Management
15.3 The quantity of chemicals purchased is based on expected usage during its shelf life
and disposal cost of unused material. Actual reagent preparation volumes reflect
anticipated usage and reagent stability.
15.4 Excess reagents, samples and method process wastes are characterized and disposed
of in an acceptable manner. For further information on waste management consult the
current version of ALL-S-002, Waste Handling.
15.5 The laboratory Chemical Hygiene Plan/Health and Safety Plan contains additional
information on pollution prevention.
16 References
16.3 USEPA, SW-846, Method 8082, "Polychlorinated Biphenyls (PCBs) by Gas
Chromatography", December 1996.
16.4 USEPA, SW-846, Method 800013, "Determinative Chromatographic Separations",
December 1996.
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16.5 Pace Analytical Services, Inc - Green Bay, SOP ALL-0-003/ALL-GB-0-003,
"Separatory Funnel Extraction of Water Samples for Semivolatile Analysis" and
"Separatory Funnel Extraction of Water Samples for Semivolatile Analysis Green
Bay Addendum".
16.6 Pace Analytical Services, Inc - Green Bay, SOP ALL-0-005/ALL-GB-0-005,
"Ultrasonic Extraction of Solid Samples for Semivolatiles Analysis" and "Ultrasonic
Extraction of Solid Samples for Semivolatiles Analysis Green Bay Addendum".
16.7 Pace Analytical Services, Inc - Green Bay, SOP GB-0-031, "Extraction of Biological
Samples for Organochlorine Pesticides/PCBs".
16.8 Pace Analytical Services, Inc - Green Bay, SOP GB-0-040, "Extraction of Wipes
and Oil for PCB Analysis".
16.9 Pace Analytical Services, Inc - Green Bay, SOP GB-0-041, "Extraction of PCBs
Using the Automated Soxhlet".
16.10 Pace Analytical Services, Inc - Green Bay, SOP GB-0-032, "Gel Permeation
Chromatography".
16.11 Pace Analytical Services, Inc - Green Bay, SOP GB-0-034, "Sulfuric Acid Cleanup".
16.12 Pace Analytical Services, Inc - Green Bay, SOP GB-0-035, "Mercury Cleanup for
the Removal of Sulfur from PCB Samples".
16.13 Pace Analytical Services, Inc - Green Bay, SOP GB-0-036, "Florisil Cleanup for
PCBs".
16.14 Pace Analytical Services, Inc - Green Bay, SOP GB-0-038, "Silica Gel Cleanup of
Organochlorine Pesticides and PCBs".
16.15 Pace Analytical Services, Inc - Green Bay, SOP GB-0-039, "Copper Cleanup for the
Removal of Sulfur from PCB Samples".
17
Tables, Diagrams, Flowcharts, Appendices, Addenda etc.
17.3 Table A. Reporting Limits for PCBs.

Arodor
CAS # Water
PRL
Soil PR1.
Biota PRL
AR1016 12674-11-2 1.0 50 50
AR1221 11104-28-2 1.0 50 50
AR1232 11141-16-5 1.0 50 50
AR1242 53469-21-9 1.0 50 50
AR1248 12672-29-6 1.0 50 50
AR1254 11097-69-1 1.0 50 50
AR1260 11096-82-5 1.0 50 50
AR1262 37324-23-5 1.0 50 50
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AR1268 11100-14-4 1.0 50 50
17.4 Table B. Solvents.
Reahent Puritv Manufacturer Vendor Cataloo YY
Hexane NS Grade Burdick & Jackson MG Scientific B&J-217-4
Acetone Pesticide Grade Burdick & Jackson MG Scientific B&J-010-4
17.5 Table C. Standard Stock Solutions.
17.6
Standard (?'oncentration 3lanufacturer Cataloo #
Pesticide Surrogate Mix 200µg/mL each in Acetone Restek Corporation or 32000
equivalent
Aroclor 1016 Mix 1000µg/mL in Hexane Restek Corporation or 32006
equivalent
Aroclor 1221 Mix 1000µg/mL in Hexane Restek Corporation or 32007
equivalent
Aroclor 1232 Mix 1000µg/mL in Hexane Restek Corporation or 32008
equivalent
Aroclor 1242 Mix 1000µg/mL in Hexane Restek Corporation or 32009
equivalent
Aroclor 1248 Mix 1000µg/mL in Hexane Restek Corporation or 32010
equivalent
Aroclor 1254 Mix 1000µg/mL in Hexane Restek Corporation or 32011
equivalent
Aroclor 1260 Mix 1000µg/mL in Hexane Restek Corporation or 32012
equivalent
Aroclor 1262 Mix 1000µg/mL in Hexane Restek Corporation or 32409
equivalent
Aroclor 1268 Mix 1000µg/mL in Hexane Restek Corporation or 32410
equivalent
Aroclor 1016 1000µg/mL in Isooctane Supelco or equivalent 4-8097
Aroclor 1260 1000µg/mL in Isooctane Supelco or equivalent 4-4809
17.7 Table D. Preparation of Analytical Standard Solutions.
Standard or 1olumc of Final Volume Final
Analctical Standard Stock Solution Standard or S' Solvent
Concentration Expiration Datc
t'scd Stuck Used t cd
1MX/L)Cb Mock Solution Pesticide luuu[tL 2umL of iuµgimL i year from date of
Surrogate Mix Hexane preparation
AR1221 Stock Solution Aroclor 1221 Mix 1000µL IOmL of 100pg/mL I year from date of
Hexane preparation
AR1232 Stock Solution Aroclor 1232 Mix 1000µL IOmL of 100µg/mL 1 year from date of
Hexane preparation
AR1242 Stock Solution Aroclor 1242 Mix 1000µL l OmL of 100µg/mL 1 year from date of
Hexane preparation
AR1248 Stock Solution Aroclor 1248 Mix 1000µL l OmL of 100µg/mL 1 year from date of
Hexane preparation
AR1254 Stock Solution Aroclor 1254 Mix 10001tL l OmL of 100µg/mL 1 year from date of
Hexane preparation
AR1262 Stock Solution Aroclor 1262 Mix 1000µL IOmL of 100µg/ml- 1 year from date of
Hexane preparation
AR1268 Stock Solution Aroclor 1268 Mix 1000µL l OmL of 100µg/mL 1 year from date of
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Hexane preparation
AR1660 Stock Solution Aroclor 1016 Mix 1000µL each IOmL of 100µg/mL each 1 year from date of
Aroclor 1260 Mix Hexane preparation
AR1660 ICV Stock Aroclor 1016 1000µL each IOmL of 100µg/mL each I year from date of
Solution Aroclor 1260 Hexane preparation
AR1221-3 Calibration AR1221 Stock AR1221 IOOmL of AR1221 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05gg/mL
AR1232-3 Calibration AR1232 Stock AR1232 IOOmL of AR1232 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
AR1242-3 Calibration AR1242 Stock AR1242 I OOmL of AR1242 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
AR1248-3 Calibration AR1248 Stock AR1248 I OOmL of AR1248 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
AR1254-3 Calibration AR1254 Stock AR1254 IOOmL of AR1254 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500gL 0.05µg/mL
AR1262-3 Calibration AR1262 Stock AR1262 I OOmL of AR1262 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
AR1268-3 Calibration AR1268 Stock AR1268 IOOmL of AR1268 6 mo. from date of
Standard Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
AR1660-1 Calibration AR1660 Stock AR1660 I OOmL of AR1660 6 mo. from date of
Standard Solution 100µL Hexane 0.1ltg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 100µL 0.01 µg/mL
AR1660-2 Calibration AR1660 Stock AR1660 IOOmL of AR1660 6 mo. from date of
Standard Solution 300µL Hexane 0.3µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 200µL 0.02µg/mL
AR1660-3 Calibration AR1660 Stock AR1660 200mL of ARI660 6 mo. from date of
Standard Solution 1000µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 1000µL 0.05µg/mL

Standard or Vulunic of Final % olumc

Anat}tical Standard
Stock Solution
Standard or
& SUlccot Final
Expiration Datc
Concentration
I set] Stock t sed Used
AR1660-4 Calibration AR166U Stock AR1660 1 UUmL of ARI66U 6 mo. from date of
Standard Solution 800µL Hexane 0.8µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 1000µL 0.10µg/mL
AR1660-5 Calibration AR1660 Stock AR1660 I OOmL of AR1660 6 mo. from date of
Standard Solution 1000µL Hexane 1.0µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 1500µL 0.15gg/mL
AR1660-3 ICV AR1660 ICV AR1660 100mL of AR1660 6 mo. from date of
Calibration Standard Stock Solution 500µL Hexane 0.5µg/mL preparation
TMX/DCB Stock TMX/DCB TMX/DCB
Solution 500µL 0.05µg/mL
18 Revisions
Pace Analytical Services, Inc. - Green Bay Laboratory
Analysis of PCBs by GC
S-GB-0-026-Rev.1
File: S-GB-0-026Revl.doc
Date: May 3, 2007
Page 18 of 18
Revision Number Reason for Change Date
GB-0-026-Rev.0 First Issue. 23May2006
Changed references of "Assistant General Manager" to "General
GB-0-026-Rev.1 Manager." Added references to SW846 prep methods. Added 03May2007
references to prep and cleanup SOPs. Added references to Ar1262 and
Ar1268 in ICAL.
Pace Analytical Services, Inc.
1241 Bellevue Street
ace Analytical M Green Bay, WI 54302
www.pacelabs.com
Phone: [phone]
l Fax: [phone]
STANDARD OPERATING PROCEDURE
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
Reference Methods: SW-846 Method 3540C
SOP NUMBER:
EFFECTIVE DATE:
SUPERSEDES:
GB-0-031-Rev.0
Date of Final Signature
KM-0-001-Rev.0
APPROVAL
qXA ?? d
Nils Melberg, Genera anager Date

Arthur F. Lautenbach, Quality Manager
a I C- 16-7
Date
© 2002 - 2007 Pace Analytical Services, Inc. This Standard Operating Procedure may not be reproduced, in part or in full,
without written consent of Pace Analytical Services, Inc. Whether distributed internally or as a "courtesy copy" to clients or
regulatory agencies, this document is considered confidential and proprietary information.
Any printed documents in use within a Pace Analytical Services, Inc. laboratory have been reviewed and approved by the persons
listed on the cover page. They can only be deemed official if proper signatures are present. `
This is COPY# G distributed on Bl fIL/C? by 4,;:L-
This is CONTROLLED or x UNCONTROLLED.
GB-0-031-Rev.0
Table of Contents
1. Purpose ...................................................................................................................................... 3
2. Scope and Application ..............................................................................................................3
3. Summary of Methods ................................................................................................................3
4. Interferences .............................................................................................................................. 3
5. Safe ......................................................................................................................................... 3
6. Definitions ................................................................................................................................. 4
7. Responsibilities and Distribution .............................................................................................. 5
8. Sample Collection, Preservation and Handling ........................................................................5
9. Equipment and Supplies .......................................................................................................... ..5
10. Reagents and Standards ........................................................................................................... ..6
11. Calibration ............................................................................................................................... ..7
12. Procedure ................................................................................................................................. ..7
13. Qualily Control ........................................................................................................................ ..9
14. Method Performance ............................................................................................................... 10
15. Pollution Prevention and Waste Management ........................................................................ 10
16. References ............................................................................................................................... 10
17. Tables Diagrams Flowcharts, Attachments, Appendices, Etc .............................................. 11
18. Revisions ................................................................................................................................. 11
Pace Analytical Services, Inc. - Green Bay Laboratory
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
GB-0-031-rev.0
1. Purpose
File: GB-O-031Rev.0.doc
Date: February 08, 2007
Paae 3 or 11
1.1 The purpose of this Standard Operating Procedure (SOP) is to describe the extraction of
homogenized biological tissue and plant samples compliant with SW-846 Method 3540C
for Organochlorine pesticide and/or PCB analysis.
2. Scope and Application
2.1. This procedure is applicable to extraction and concentration of Organochlorine pesticides
and PCBs from homogenized biological tissue and plant samples. Extracts may be
prepared by this method for analysis by several chromatographic methods including, but
not limited to, SW-846 Methods 8081A and 8082.
2.2. The policies and procedures contained in this SOP are applicable to all personnel
involved in the preparation of extracts for chromatographic analysis.
3. Summary of Methods
3.1. Approximately 20 grams of homogenized tissue or plant sample is mixed with sodium
sulfate and extracted with methylene chloride for a minimum of 16 hours in a soxhlet
extractor. The methylene chloride extracts are then concentrated, exchanged to hexane
(dependent upon further extract cleanup) and concentrated to a volume of 10 mL.
4. Interferences
4.1. Interferences may be introduced into sample extracts by contaminants in solvents,
reagents, glassware, and any other material that comes in contact with the sample or
extract during extract preparation. These interferences must be closely monitored by
analyzing Method Blank samples and taking corrective action as required.
4.2 Interferences co-extracted from samples will vary considerably depending on the source
of the material. Contaminants that may interfere with the analysis may be removed from
the extracts using any combination of cleanups including, but not limited to Gel
Permeation Chromatography (GPC), Florisil column cleanup, Florisil cartridge cleanup,
and Silica Gel Separation. These cleanup procedures are described in separate SOPs.
5. Safety
5.1. The toxicity or carcinogenicity of each reagent used in this method has not been fully
established. Each chemical should be regarded as a potential health hazard and exposure
should be as low as reasonably achievable. Cautions are included for known extremely
hazardous material.
5.2. A reference file of Material Safety Data Sheets (MSDS) is made available to all
personnel involved in the chemical analysis, and is located at the front desk. A formal
safety plan has been prepared and is distributed to all personnel with documented
training.
5.3. The use of personal protective equipment (gloves, lab coats and safety glasses) is
required when handling samples.
Pace Analytical Services, Inc. - Green Bay Laboratory
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
GB-0-031-rev.0
6. Definitions
File: GB-O-031Rev.0.doc
Date: February 08, 2007
Paae 4 or 11
6.1. Refer to Section 10.0 of the most current version of the Pace Quality Manual for the
terms used at Pace Analytical. When definitions are not consistent with NELAC defined
terms, an explanation will be provided in this SOP.
6.2. Duplicate Sample - A second aliquot of the same environmental sample analyzed in the
same manner as the original sample in order to evaluate precision.
6.3. Laboratory Control Sample (LCS) - A blank matrix sample spiked with a known
concentration of analytes of interest. The material is from a second source (not from same
as calibration material). Laboratory accuracy is evaluated using the LCS. Refer to the
determinative SOP for corrective action and contingencies for handling out of control
data.
6.4. Laboratory Information Management System (LIMS) - A system for transferring,
processing, storing, and reporting analysis results.
6.5. Lot - A quantity of bulk material of similar composition processed or manufactured at
the same time.
6.6. Matrix Spike (MS) - An aliquot of an environmental sample spiked with known
quantities of specified target compounds and subjected to the entire sample preparation
and analysis procedure. The analysis results from a matrix spike sample are compared to
results from an unspiked aliquot of the same sample to determine recovery of the spike
from the sample matrix. Refer to the determinative SOP for corrective action and
contingencies for handling out of control data. The sample used for the MS/D pair is
either determined by the client or selected at random from client samples as sample
volume allows.
6.7. Matrix Spike Duplicate (MSD) - A second aliquot of the sample that is treated the same
as the original matrix spike sample. The relative percent difference between the matrix
spike and matrix spike duplicate is calculated and used to assess method precision. Refer
to the determinative SOP for corrective action and contingencies for handling out of
control data.
6.8. Method Blank (MB) - A blank sample prepared in the laboratory containing all reagents
and internal standards and is carried through the entire analytical procedure. The method
blank is used to evaluate laboratory background and contamination. Refer to the
determinative SOP for corrective action and contingencies for handling out of control
data.
6.9. Method Detection Limit (MDL) - The minimum concentration of a substance that can
be measured and reported with 99% confidence that the analyte concentration is greater
than zero. MDLs are determined by analyzing replicate spike samples prepared by the
lab and taken through all preparation and analysis steps of the method. The method
detection limit is calculated using the appropriate Student's t-parameter times the
standard deviation of a series of spiked samples. MDL study information is located in the
quality assurance office.
Pace Analytical Services, Inc. - Green Bay Laboratory File: GB-0-0311tev.0.doc
Extraction of Biological Samples for Organochlorine Pesticides/PCBs Date: February 08, 2007
GB-0-031-rev.0 Page 5 or 11
7. Responsibilities and Distribution
7.1. Analyst - Any analyst using this procedure is responsible for reading, understanding, and
following this SOP. Any deviation from this SOP must be reported to the appropriate
supervisor. The analyst must make their recommendations for changing the SOP to their
supervisor or the QM in writing.
7.2. General Manager - The General Manager has overall responsibility for ensuring that
SOPS are prepared and implemented for all activities appropriate to the laboratory. The
General Manager must ensure that all analysts are properly trained and qualified to use
this procedure. The General Manager is also responsible to ensure that the SOP is
followed. The General Manager is responsible for reviewing the SOP and
communicating recommended changes to the QM. The General Manager shall review
and approve all SOPS.
7.3. Quality Manager (QM) - The QM is responsible for monitoring the implementation of
the SOPS. The QM shall participate in the revision of the SOP and make sure it is
current. The QM shall review and approve all SOPS.
7.4. Distribution - The official version of this SOP is the signed hardcopy version found in
the laboratory. A copy of the SOP shall be kept in the department for reference.
7.5. Revision - This SOP shall be reviewed every two years at a minimum. Independent of
the minimum review frequency, revisions shall be incorporated as needed if procedures
or methods change.
8. Sample Collection, Preservation, and Handling
8.1. The homogenized samples must be kept frozen in glass jars.
8.2. Extracts should be stored at 4°t2°C in the dark in Teflon-sealed containers until analysis
is complete. The sample extracts must be analyzed within 40 days from extraction.
9. Equipment and Supplies
9.1. Soxhlet extractors: 55 mm inner diameter X 340 mm length holding cell with heaters and
cold water condensers
9.2. Concentrator tubes: Kuderna-Danish, 10 ml, graduated (Kontes K-570050-1025 or
equivalent)
9.3. Evaporation flasks: Kuderna-Danish 500 ml (Reliance G-9601-001 or equivalent)
9.4. Snyder columns: Kudema-Danish, three-ball macro (Kontes K-503000-0121 or
equivalent)
9.5. Culture tubes: 15 ml and 9 ml with Teflon-lined screw cap
9.6. Boiling chips: Teflon or pre-rinsed silicone carbide
9.7. Sodium Sulfate (Na2SO4): Preheated at 400°C for 4 hours in a crucible to remove
Pace Analytical Services, Inc. - Green Bay Laboratory
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
GB-0-031-rev.0
contaminants
File: GB-0-031Rev.O.doc
Date: February 08, 2007
Paae 6 or 11
9.8. Water bath: Heated, with concentric ring cover, capable of temperature control within
+5°C. The bath should be used in a hood.
9.9. Syringes: 250-1000µL Gastight syringes (Hamilton 1000 series or equivalent)
9.10. Beakers: 250 mL
9.11. Erlenmeyer flasks: 500 mL
9.12. Glass wool
9.13. Stainless steel spatulas
9.14. Analytical balance: Capable of weighing 300g+ 0.01g
9.15. Disposable Pasteur pipettes
10. Reagents and Standards
10.1. Methylene chloride, pesticide grade
10.2. Acetone, pesticide grade
10.3. Hexane, pesticide grade
10.4. Surrogate spiking solution: See Table 1 for standard preparation.
10.5. Matrix spiking solution: Dependent upon analysis requested. See Table 1 for standard
preparation.
Table 1
Standard Stock Standard Conc. Amount Final Solvent Final
Used Volume Used, Conc.
Surrogate spiking solution TMX (Tetrachloro-m-xylene) 200gg/mL 10 mL 1000 mL Acetone 2.01ig/mL
and DCB Decachlorobi henyl
PCB Matrix Spike One of either Aroclor 1016, 1000 gg/ml 1000 gL 200 mL Acetone 5.0gg/mL
1242, 1248, 1254, or 1260

Pesticide Matrix Spike Custom Pesticide Mix A and
Custom Pesticide Mix B
5.0 - 50 gg/ml 2000 gL each
of Mix A and
25 mL
Acetone 0.4-
4.0gg/mL
Mix B
Toxaphene Matrix Spike Toxaphene Mix 1000 gg/ml 2500 gL 50 mL Acetone 50.0gg/mL
Historical data or requirements of specific projects may determine the analytes and concentrations added to the sample spikes.
Custom Pesticide Mix A contains alpha-BHC, gamma-BHC, Heptachlor, Endosulfan I, Dieldrin, Endrin, 4,4'-DDD, 4,4'-DDT,
and Methoxychlor.
Custom Pesticide Mix B contains beta-BHC, delta-BHC, Aldrin, Heptachlor epoxide, alpha-chlordane, gamma-chlordane, 4,4'-
DDE, Endosulfan II, Endrin aldehyde, Endosulfan sulfate, and Endrin ketone.
Pace Analytical Services, Inc. - Green Bay Laboratory
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
GB-0-031-rev.0
11. Calibration
File: GB-0-031Rev.O.doc
Date: February 08, 2007
Page 7 or 11
11.1 The analytical balance used during this procedure must be calibrated prior to use each
day. Refer to the current revision of Support Equipment (ALL-Q-013) for how to
calibrate a balance.
12. Procedure
12.1. Extraction
12.1.1. Attach Soxhlet extractors (55 mm i.d. X 340 mm length) to 500-mL Erlenmeyer
flasks with ground glass joints.
12.1.2. Add two plugs of glass wool to each extractor, one to cover the bottom to prevent
sample from entering the solvent return arm and the other to cover the top of the
sample.
12.1.3. Add 300 mL of glass-distilled Methylene chloride to the Erlenmeyer flask, along
with about five boiling chips. Attach the Erlenmeyer to the Soxhlet extractor.
12.1.4. Attach the extractors to the condensers in the fume hood.
12.1.5. Adjust the temperature so the extractors cycle at a rate of 12 to 15 cycles/hour.
12.1.6. Allow the extractors to rinse for 4 hours, then shut off the heaters and allow them to
cool.
12.1.7. Remove the condensers and drain all the solvent remaining in the extractors into the
Erlenmeyer flask.
12.1.8. Discard the solvent and add new boiling chips to Erlenmeyer flask.
12.1.9. The extractors are now ready for the samples.
12.1.10. Weigh 20g of sodium sulfate into a 250-mL beaker; this will represent the method
blank. Weigh 20g of the control matrix into a second 250-mL breaker; this will be
used for the control spike. Weigh 20g samples into separate 250-mL beakers.
Record the actual weight in the extraction logbook.
12.1.11. Add 40g of anhydrous sodium sulfate to each beaker and mix. More sodium sulfate
may be necessary: when a sufficient amount has been added, the sample will appear
granular.
12.1.12. Place the beakers in a fume hood and let them dry, stirring occasionally.
12.1.13. Remove the top glass wool plug from the Soxhlet extractors that have been pre-
rinsed.
12.1.14. Transfer the entire sample from the beaker to the extractor and place the glass wool
plug on top. The sample level in the extractor should not exceed the top of the
solvent return arm; this will keep the entire sample immersed in solvent during the
extraction process. Rinse the sample beaker with McC12 and add to the top of the
Soxhlet extractor.
Pace Analytical Services, Inc. - Green Bay Laboratory File: GB-O-031Rev.0.doc
Extraction of Biological Samples for Organochlorine Pesticides/PCBs Date: February 08, 2007
GB-0-031-rev.0 Page 8 or 11
12.1.15. Add 500 gL of the 2.0 gg/mL surrogate spiking solution to all samples, laboratory
control spikes, matrix spikes, and method blanks. (The amount of surrogate spiking
solution added may need to be adjusted for the final volume of the sample extract.)
12.1.16. Add the appropriate amount of Matrix Spike solution(s) to the laboratory control
spikes and matrix spikes. This will depend upon the analytes of interest and project
specific requirements. (The amount of matrix spike solution added may need to be
adjusted for the final volume of the sample extract.)
12.1.16.1. For pesticide analysis add 1000 gL of the 0.4 - 4.0 gg/mL Pesticide
Matrix Spike solution.
12.1.16.2. For PCB analysis add 1000 gL of the 5.0 gg/mL PCB Matrix Spike
solution.
12.1.16.3. For Toxaphene analysis add 800 gL of the 50 gg/mL Toxaphene Matrix
Spike solution.
12.1.16.4. Additional compounds which may be added include 2,4-DDT, 2,4-DDD,
2,4-DDE, Hexachlorobenzene, Pentachloroanisole, Oxychlordane, Trans-
nonachlor, Cis-nonachlor, and Mirex.
12.1.17.Add 350 mL of glass-distilled methylene chloride to each Soxhlet extractor.
12.1.18.Attach the condensers and set the temperature so that the extractors cycle at a rate
of 12 to 15 cycles per hour.
12.1.19.Let the extractors cycle for 16 hours.
12.1.20.After 16 hours shut off the heating elements and allow the samples to cool.
12.1.21.Rinse the extractor with about 50 mL of Methylene chloride and drain it into the
collection Erlenmeyer flask.
12.1.22.Drain all solvent remaining in the extractor into the Erlenmeyer flask.
12.2. Concentration
12.2.1. Assemble a K-D concentrator by attaching a 10-mL concentrator tube to a 500 mL
evaporative flask. Other concentration devices or techniques may be used in place
of the K-D if equivalency is demonstrated for all analytes of interest.
12.2.2. Pour the extracts into the K-D concentrators. Rinse the Erlenmeyer flasks with
20 to 30 mL of methylene chloride to complete the quantitative transfer.
12.2.3. Add one or two clean boiling chips to the evaporative flasks and attach a three-
ball Snyder column. Place the K-D apparatus on a hot water bath (100°C to
105°C) so that the concentrator tube is partially immersed in the hot water and
the entire lower rounded surface of the flask is bathed with hot water and the
entire lower rounded surface of the flask is bathed with hot vapor. Adjust the
vertical position of the apparatuses and the water temperature as required to
complete the concentration in 10 to 15 minutes. At the proper rate of distillation,
the balls of the column will actively chatter but the chambers will not flood with
condensed solvent. When the apparent volume of liquid reaches 5 to 10 mL,
remove the K-D apparatus. Allow it to drain and cool for at least 10 minutes.
Pace Analytical Services, Inc. - Green Bay Laboratory File: GB-0-031Rev.O.doc
Extraction of Biological Samples for Organochlorine Pesticides/PCBs Date: February 08, 2007
GB-0-031-rev.0 Page 9 or 11
12.2.4. Adjust the volume to 10 mL using methylene chloride.
12.2.5. Samples that are to be analyzed for PCBs only will require the extracts to be
exchanged to hexane. For these extracts, add approximately 50 ML of hexane to
the K-D apparatus and continue concentration to a volume of 4-6 mL. Remove
the K-D apparatus from the water bath and allow it to drain and cool for at least
10 minutes or until extracts have cooled to air temperature. Adjust the final
volume to 10 mL using hexane.
12.3. Extract Cleanups
12.3.1. Lipid Determination: One milliliter of the extract is used to determine the percent
lipids using SOP KM-L-003-Rev.0. The remaining nine milliliters should go
through the following cleanups necessary for the required analysis.
12.3.2. GPC Cleanup of Extracts: Sample extracts requiring pesticide and PCB analysis
should have contaminants removed using gel permeation chromatography. This
cleanup is not necessary for samples requiring only PCB analysis because the
Florisil column cleanup procedure is validated specifically to remove contaminants
from the PCBs.
12.3.3. Florisil Column Cleanup of Extracts for PCBs: Extracts requiring only PCB
analysis should be cleaned using column chromatography with Florisil.
12.3.4. Florisil Cartridge Cleanup for pesticides: Extracts requiring pesticide analysis may
be cleaned using Florisil cartridge cleanup.
12.3.5. Silica Gel Separation of Pesticides and PCBs: Extracts which are to be analyzed for
both pesticides and PCBs may have the PCBs separated from the majority of the
pesticides using column chromatography with silica gel. Extracts may be screened
prior to this cleanup to determine if PCBs will cause a problem with the
identification of pesticides in the extract. If PCBs are not present, or present at
levels which will not interfere with pesticide analysis, this cleanup is not necessary.
13. Quality Control
13.1 One method blank is extracted per 20 samples OR per extraction batch, whichever is
more frequent. The method blank should be blank sodium sulfate or an analyte-free biota
matrix such as tuna fish for animal extractions or alfalfa for plant analyses.
13.2 A laboratory control spike is extracted per 20 samples OR per extraction batch whichever
is more frequent. Control spikes are usually prepared using analyte-free tuna fish for
animal analysis or alfalfa for plant analyses. The control spike is fortified with a
representative list of the analytes of interest.
13.3 A matrix spike and a matrix spike duplicate must be performed for every 20 samples
when appropriate sample volume is present, otherwise a laboratory control spike
duplicate will be performed. Matrix spikes are used to indicate matrix effects on the
analysis of the analytes of interest. The sample used for the MS/D pair is either
Pace Analytical Services, Inc. - Green Bay Laboratory File: GB-O-031Rev.0.doc
Extraction of Biological Samples for Organochlorine Pesticides/PCBs Date: February 08, 2007
GB-0-031-rev.0 Page 10 or 11
determined by the client or selected at random from client samples as sample
volume allows
13.4 Surrogate standards must be added to all samples, laboratory control spikes, matrix
spikes, and method blanks prior to extraction. Surrogates are used to monitor the
efficiency of the method on each sample and possible matrix related effects.
13.5 All quality control samples (MB, LCS, MS, MSD, and duplicate samples) must be
analyzed by the same determinative methods as the samples in the batch. The acceptance
criteria and corrective actions are described in the determinative method SOPS.
14. Method Performance
14.1 There are several requirements that must be met to insure that this procedure generates
accurate and reliable data. A general outline of requirements has been summarized below.
Further specifications may be found in the Laboratory Quality Manual.
14.2 The analyst must read and understand this procedure with written documentation
maintained in his/her training file.
14.3 An initial demonstration of capability (IDC) must be performed per All-Q-020, Training
Procedures. A record of the IDC will be maintained in his/her QA file with written
authorization from the Laboratory Manager and Quality Manager.
14.4 An annual method detection limit (MDL) study will be completed per ALL-Q-004, Method
Detection Limit Studies, for this method and whenever there is a major change in personnel
or equipment. The results of these studies are retained in the quality assurance office.
14.5 Periodic performance evaluation (PE) samples are analyzed per ALL-Q-010, PE/PT
Program, to demonstrate continuing competence. All results are stored in the QA office.
15. Pollution Prevention and Waste Management
15.1 The quantity of chemicals purchased is based on expected usage during its shelf life
and disposal cost of unused material. Actual reagent preparation volumes reflect
anticipated usage and reagent stability.
15.2 Excess reagents, samples and method process wastes are characterized and disposed
of in an acceptable manner. For further information on waste management consult the
current version of ALL-S-002, Waste Handling.
15.3 The laboratory Chemical Hygiene Plan/Health and Safety Plan contains additional
information on pollution prevention.
16. References
16.1. USEPA, SW-846, Method 3540C, "Soxhlet Extraction", December 1996.
Pace Analytical Services, Inc. - Green Bay Laboratory
Extraction of Biological Samples for Organochlorine Pesticides/PCBs
GB-0-031-rev.0
17. Tables, Diagrams, Flowcharts, Appendices, etc.
Not Applicable
18. Revisions
File: GB-O-031Rev.0.doc
Date: February 08, 2007
Page 11 or 11
Document Number Reason for Change Date
Converted SVO 60 Rev 1 to new format.
KM-0-001-rev.0 January 20, 2005
Incorporated associated cleanup method references.
Converted to Green Bay SOP
GB-0-031-rev.0 Update General Manager and Quality Manager February 08, 2007
Added correct SOPs to Sections 11, 14, 15
Section 13.3 Added procedure for selecting MS/MSD
Method Detection Reporting Limits
Method 1668A
ceARalyticalry ; nelac s
( /?A?
Tissue

Analyte Method
Detection Limit
(pp0
Reporting
Limit (ppt) LCS Criteria
Lower Control
Limit (%) LCS Criteria
Upper Control
Limits (%)
% RPD
Limit
PCB-1 7.7 50 50 150 30
PCB-2 18.6 50 50 150 30
PCB-3 5.6 50 50 150 30
PCB-4 22.1 50 50 150 30
PCB-5 14.1 50 50 150 30
PCB-6 6.8 50 50 150 30
PCB-7 7.1 50 50 150 30
PCB-8 22.7 50 50 150 30
PCB-9 5.7 50 50 150 30
PCB-10 17.3 50 50 150 30
PCB-11 77.2 155 50 150 30
PCB-12/13 16.8 50 50 150 30
PCB-14 7.5 50 50 150 30
PCB-15 25.7 52 50 150 30
PCB-16 14.0 50 50 150 30
PCB-17 14.8 50 50 150 30
PCB-18/30 18.5 50 50 150 30
PCB-19 5.4 50 50 150 30
PCB-20/28 65.0 130 50 150 30
PCB-21/23 25.8 54 50 150 30
PCB-22 29.1 60 50 150 30
PCB-23 4.7 50 50 150 30
PCB-24 6.9 50 50 150 30
PCB-25 7.3 50 50 150 30
PCB-26/29 21.9 50 50 150 30
PCB-27 6.6 50 50 150 30
PCB-31 52.6 106 50 150 30
PCB-32 10.9 50 50 150 30
PCB-34 5.7 50 50 150 30
PCB-35 7.3 50 50 150 30
PCB-36 4.8 50 50 150 30
PCB-37 36.8 75 50 150 30
PCB-38 5.5 50 50 150 30
PCB-39 6.4 50 50 150 30
PCB-40/41/71 71.6 150 50 150 30
PCB-42 35.3 75 50 150 30
PCB-43 18.3 50 50 150 30
PCB-44/47/65 97.8 200 50 150 30
PCB-45/51 25.7 55 50 150 30
PCB-46 28.7 60 50 150 30
PCB-48 36.2 75 50 150 30
PCB-49/69 61.3 125 50 150 30
PCB-50/53 41.8 90 50 150 30
Pace Analytical Services 1 1700 Elm Street I Minneapolis, MN 55414 1 [phone] 1 [phone] (fax) I wvvw.pacelabs.com
Method Detection Reporting Limits
Method 1668A
1--!2WAr1aMkar nela
Tissue

Analyte Method
Detection Limit
(pp0
Reporting
Limit (ppt) LCS Criteria
Lower Control
Limit (%) LCS Criteria
Upper Control
Limits (%)
% RPD
Limit
PCB-52 81.4 165 50 150 30
PCB-54 5.9 50 50 150 30
PCB-55 22.0 50 50 150 30
PCB-56 28.8 60 50 150 30
PCB-57 26.4 55 50 150 30
PCB-58 7.0 50 50 150 30
PCB-59/62/75 64.7 130 50 150 30
PCB-60 20.5 50 50 150 30
PCB-61/70/74/76 92.8 200 50 150 30
PCB-63 9.4 50 50 150 30
PCB-64 59.1 120 50 150 30
PCB-66 70.9 150 50 150 30
PCB-67 13.1 50 50 150 30
PCB-68 9.1 50 50 150 30
PCB-72 11.3 50 50 150 30
PCB-73 17.6 50 50 150 30
PCB-77 5.2 50 50 150 30
PCB-78 6.2 50 50 150 30
PCB-79 13.1 50 50 150 30
PCB-80 17.2 50 50 150 30
PCB-81 3.9 50 50 150 30
PCB-82 14.9 50 50 150 30
PCB-83 22.1 50 50 150 30
PCB-84 19.1 50 50 150 30
PCB-85/116/117 23.5 50 50 150 30
PCB-86/87/97/108/119/125 52.0 110 50 150 30
PCB-88/91 14.4 50 50 150 30
PCB-89 6.3 50 50 150 30
PCB-90/101/113 93.6 200 50 150 30
PCB-92 12.2 50 50 150 30
PCB-93/98/100/102 94.1 200 50 150 30
PCB-94 14.6 50 50 150 30
PCB-95 11.6 180 50 150 30
PCB-96 16.0 50 50 150 30
PCB-99 23.9 50 50 150 30
PCB-103 16.8 50 50 150 30
PCB-104 4.5 50 50 150 30
PCB-105 26.2 55 50 150 30
PCB-106 20.3 50 50 150 30
PCB-107/124 43.6 100 50 150 30
PCB-109 11.3 70 50 150 30
PCB-110/115 79.8 160 50 150 30
PCB-111 8.3 50 50 150 30
Pace Analytical Services 1 1700 Elm Street I Minneapolis, MN 55414 1 [phone] 1 [phone] (fax) I wvvw.pacelabs.com
Method Detection Reporting Limits
Method 1668A
/?ZAnWkar
Tissue nelac =

Analyte Method
Detection Limit
(pp0
Reporting
Limit (ppt) LCS Criteria
Lower Control
Limit (%) LCS Criteria
Upper Control
Limits (%)
% RPD
Limit
PCB-112 16.9 50 50 150 30
PCB-114 6.1 50 50 150 30
PCB-118 38.9 80 50 150 30
PCB-120 10.5 50 50 150 30
PCB-121 9.6 50 50 150 30
PCB-122 18.3 50 50 150 30
PCB-123 5.0 50 50 150 30
PCB-126 22.1 50 50 150 30
PCB-127 17.3 50 50 150 30
PCB-128/166 14.6 50 50 150 30
PCB-129/138/163 29.7 60 50 150 30
PCB-130 15.5 50 50 150 30
PCB-131 14.9 50 50 150 30
PCB-132 20.2 50 50 150 30
PCB-133 9.3 50 50 150 30
PCB-134/143 17.3 50 50 150 30
PCB-135/151 52.1 105 50 150 30
PCB-136 18.1 50 50 150 30
PCB-137 12.9 50 50 150 30
PCB-139/140 55.9 115 50 150 30
PCB-141 23.2 50 50 150 30
PCB-142 21.6 50 50 150 30
PCB-144 34.9 70 50 150 30
PCB-145 8.1 50 50 150 30
PCB-146 14.5 50 50 150 30
PCB-147/149 75.9 160 50 150 30
PCB-148 10.8 50 50 150 30
PCB-150 11.9 50 50 150 30
PCB-152 10.0 50 50 150 30
PCB-153/168 58.6 120 50 150 30
PCB-154 9.7 50 50 150 30
PCB-155 4.2 50 50 150 30
PCB-156/157 13.3 50 50 150 30
PCB-158 8.2 50 50 150 30
PCB-159 12.2 50 50 150 30
PCB-160 17.7 50 50 150 30
PCB-161 17.8 50 50 150 30
PCB-162 4.9 50 50 150 30
PCB-164 21.7 50 50 150 30
PCB-165 17.2 50 50 150 30
PCB-167 7.8 50 50 150 30
PCB-169 6.2 50 50 150 30
PCB-170 13.3 50 50 150 30
PCB-171/173 19.1 50 50 150 30
Pace Analytical Services 1 1700 Elm Street I Minneapolis, MN 55414 1 [phone] 1 [phone] (fax) I wvvw.pacelabs.com
Method Detection Reporting Limits
Method 1668A
Tissue

n(1?20AWWRI-

Analyte Method
Detection Limit
(pp0
Reporting
Limit (ppt) LCS Criteria
Lower Control
Limit (%) LCS Criteria
Upper Control
Limits (%)
% RPD
Limit
PCB-172 14.7 50 50 150 30
PCB-174 17.7 50 50 150 30
PCB-175 16.7 50 50 150 30
PCB-176 6.9 50 50 150 30
PCB-177 12.3 50 50 150 30
PCB-178 9.4 50 50 150 30
PCB-179 12.3 50 50 150 30
PCB-180/193 35.5 75 50 150 30
PCB-181 13.5 50 50 150 30
PCB-182 17.6 50 50 150 30
PCB-183/185 20.7 50 50 150 30
PCB-184 8.3 50 50 150 30
PCB-186 9.9 50 50 150 30
PCB-187 23.2 50 50 150 30
PCB-188 8.9 50 50 150 30
PCB-189 5.9 50 50 150 30
PCB-190 8.7 50 50 150 30
PCB-191 11.2 50 50 150 30
PCB-192 13.3 50 50 150 30
PCB-194 23.0 50 50 150 30
PCB-195 11.0 50 50 150 30
PCB-196 17.2 50 50 150 30
PCB-197/200 29.1 60 50 150 30
PCB-198/199 21.6 50 50 150 30
PCB-201 9.4 50 50 150 30
PCB-202 11.9 50 50 150 30
PCB-203 10.8 50 50 150 30
PCB-204 16.9 50 50 150 30
PCB-205 8.5 50 50 150 30
PCB-206 14.7 50 50 150 30
PCB-207 8.8 50 50 150 30
PCB-208 5.8 50 50 150 30
PCB-209 10.7 50 50 150 30
Pace Analytical Services 1 1700 Elm Street I Minneapolis, MN 55414 1 [phone] 1 [phone] (fax) I wvvw.pacelabs.com